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Textile Research Journal

0(00) 1–13

Application of a novel plasma-based ! The Author(s) 2019

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method of introducing maleic acid and DOI: 10.1177/0040517519845685
journals.sagepub.com/home/trj
pentaerythritol phosphate urea salt
onto polyester fabrics for durable
flame-retardant treatment

Tianchi Zhou1 , Yangyang Wang1, Haodong Xu1, Lu Cai1,

Yanchun Liu2 and Chunmei Zeng3

Abstract
In this work, a novel anti-flame poly(ethylene terephthalate) (PET) fabric was successfully fabricated by plasma-based
technology combined with pad-dry-cure treatment finishing. Low-temperature plasma can graft maleic acid (MA) onto a
PET polymer backbone, which can activate the PET fiber and provide the opportunity of reaction with pentaerythritol
phosphate urea salt (PEPAS) to achieve an excellent and durable anti-flame ability. Furthermore, the chemical reaction
between PET-MA and PEPAS can form a complex and compact net structure that can effectively improve the anti-
dripping property of PET. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning
electron microscopy analysis showed that MA and PEPAS were successfully introduced onto the surface of the PET
fabric, and a compact protective carbon layer was formed during the combustion process due to the synergistic effect of
phosphorus and nitrogen. The flame-retardant and anti-dripping properties were evaluated by thermogravimetric ana-
lysis, the limiting oxygen index (LOI) and a vertical burning test. The treated samples showed the maximum LOI value of
29.3, possessing excellent thermal stability and self-extinguishing ability and inhibiting melt-dripping ability. Moreover,
tensile strength at break of the treated PET fabric was slightly greater than that of the original PET fabric, indicating that
this type of treatment had little negative impact on the bulk of the PET fabric. After 20 laundering cycles, the LOI value of
the treated sample still remained at 26.8, which indicated durability in the flame-retarding effect.

Keywords
anti-flame, plasma, maleic acid, polyester fabric, anti-dripping

Poly(ethylene terephthalate) (PET) is the most widely
used synthetic raw material for textile industries and
possesses many excellent benefits, such as high chemical
stability, good mechanical performance, spinnability,
dyeability and low cost. However, there is still the crit-
ical problem of easy flammability and severe melt drip-
ping, which greatly limit its application in the field of
textiles.1,2 To endow PET with anti-flame and anti-
dripping properties, the many methods exploited by
scientists and engineers to impart PET anti-flame and
anti-dripping properties can be mainly divided into
three categories: introducing flame-retardant mono-
mers into PET polymer chains by copolymerization
strategies;3–5 adding flame-retardant additives, such as
phosphorus-containing agents, nanoparticles and nitro-
genous heterocyclic compounds, into PET during the
mixing process;1,6,7 using flame-retardant agents to
1
Textile and Garment College, YanCheng Institute of Technology, China
2
Key Laboratory of Clean Dyeing and Finishing Technology of Zhejiang
Province, Shaoxing University, China
3
Jiangsu R&D Center of the Ecological Dyes and Chemicals, Yancheng
Polytechnic College, China
Corresponding author:
Tianchi Zhou, Textile and Garment College, YanCheng Institute of
Technology, 1 Xi’wang middle Road, Yancheng 224051, China.
Email: 120413181@qq.com
2 Textile Research Journal 0(00)
finish PET fabrics by both physical and chemical tech-
nologies.8–10 Although the first two methods have the
advantages of easy preparation, durability, dynamic
tenability and so on, there is the main problem of the
number of flame-retardant compositions. Increasing
the proportion of active ingredients in modified PET
materials may result in negative effects on application
performances and mechanical properties, while a smal-
ler fraction of active ingredients cannot achieve the
expected anti-flame goal. In particular, using the
second method, active ingredients may apparently
leak out from modified PET fabrics due to great differ-
ences in chemical composition and poor compatibil-
ity.11 Therefore, more and more scientists and
engineers are concerned with developing more conveni-
ent and inexpensive flame-retardant treatments for PET
fabrics.
With a home-made flame-retardant poly (2-hydroxy
propylene spirocyclic pentaerythritol bisphosphonate)
(PPPBP) used to finish PET fabrics, Chen et al.12
found that the chars generated by the decomposition
of PPPBP during combustion could effectively enhance
the flame retardancy and anti-dripping performance of
the finished fabrics. With the help of the photo-induced
method, Yu et al.8 used 1-hydroxy ethylidene-
1,1-diphosphonic acid (HEDP) and sulfamic acid
combined with the pad-cure process to improve the
anti-flame properties of the PET fabric, for which the
limiting oxygen index (LOI) value could reach up to
25.9 when the grafting percent was 22.5%. With the
action of polyethyleneimine (PEI), negatively charged
oxidized sodium alginate (OSA) and hypophosphorous
acid (HA), Pan et al.13 improved the fireproof function
of polyester–cotton blend fabrics, as well as good laun-
dering durability, by a layer-by-layer assembled coating
technology and a cross-linking technology. To achieve
the activation effect of the outer surface, Younis14
exposed the PET fabrics to ultraviolet (UV)/O3 treat-
ment for a certain irradiation time and subsequently
immersed the fabrics into the coating solution to
obtain the durable anti-flame performance. According
to their findings, durability plays a vital role in flame-
retardant treatments for PET fabrics. However, so far
the durability has not been satisfactory for practical
production and further studies are still needed.
Low-temperature plasma can generate charged par-
ticles that are accelerated by the electric field to collide
on the material surface. Subsequently, these charged
particles can etch the surface of the treated polymer
material, improve the adhesion effect due to the
increased roughness, separate hydrogen from the
main chain of the polymer and create free radicals
and new active functional groups on the polymer sur-
face.15,16 Meanwhile, plasma technology can effectively
modify the material surface without hurting its bulk
properties and has characteristics such as good energy
conservation and environment protection, low cost and
being easily prepared, resulting in it being widely
applied in the textile manufacturing industry to achieve
the goals of improving the dyeing ability and fastness,
hydrophobic and hydrophilic performance, pill resist-
ance, removal of wicks, etc.17–19 The original PET
fabric (O-PET) is difficult to subject to functional fin-
ishing due to its characteristics of densification and
chemical stability, but free radicals and new active func-
tional groups can be effectively introduced onto the
PET fabric by plasma technology; thus, a durable
chemical finishing effect on the PET fabric can be suc-
cessfully obtained because of the formation of covalent
bonding, hydrogen bonding and ionic bonding.20,21
Lv et al.22 used low-temperature oxygen plasma to
etch polyester fabrics and achieved durable antistatic
and antibacterial properties. Gotoh et al.23 modified a
PET film to possess an extremely stable wet ability by
the plasma-coating-oxidation technique. Haji et al.24,25
used plasma treatment to assist in depositing amino
functionalized carbon nanotubes onto the surface of
PET fabric to improve the electrical conductivity and
microwave shielding behavior. Belhaj et al.26 employed
plasma to realize the cross-linking of sericin on polyes-
ter fabric, and the treated samples yielded a more dur-
able hydrophilic finish with a high capillarity. Tarek
et al.27 introduced two different azo pH-indicator
dyes onto the surface of PET textile to achieve halo-
chromic properties, using plasma-assisted sol–gel coat-
ing technology. Jaššo et al.28 treated PET fibers with
low-temperature nitrogen plasma to perform surface
activation, then the activated PET fibers were soaked
in a maleic acid (MA) solution to graft with MA in
order to enhance their adhesion to the styrene–butadi-
ene rubber blend.
Plasma technology also has been applied in the field of
flame retardants for synthetic fiber textiles and research-
ers always focus on the following three aspects: (a) sur-
face etching to improve the specific surface area,
introduce oxygen-containing polar functional groups
and generate free radicals; (b) polymerization induced
by plasma and the film formed on the surface of fiber;
(c) the direct grafting reaction.29,30 Carosio et al.29 pro-
vided a combination method of plasma surface activation
and montmorillonite nanoparticle adsorption to prepare
anti-flame PET fabrics, and the treated fabrics
made remarkable progress in terms of thermal stability,
time to ignition and heat release rate by comparison
with O-PETs. Tsafack and Joelle30 investigated the
argon plasma-induced graft-polymerization of four
acrylate monomers containing phosphorus, diethyl
(acryloyloxyethyl)phosphate, diethyl-2-(methacryloylox-
yethyl) phosphate, diethyl(acryloyloxymethyl) phospho-
nate and dimethyl(acryloyloxymethyl) phosphonate,
Zhou et al. 3

for the fire-proofing of polymeric substrates. Wafaa
et al.31 used dielectric barrier discharge (DBD) air
plasma treatment for fiber surface activation to facilitate
the deposition of aluminum oxide, nano-silver and nano-
titanium dioxide onto polyester fabric and the results
showed that air plasma-Al2O3 treatment obviously
improved the flame retarding effect. Plasma technology
has brought great advances in the anti-flame effect for
synthetic polymer fabrics, but there are still some short-
comings, such as weak absorption, limited functional
groups, growing less powerful with time, being easily
washed away and being difficult to synthesize.
Herein, we designed a novel anti-flame method, in
which MA was chosen as a bridge to combine PET
with pentaerythritol phosphate urea salt (PEPAS). The
plasma-induced PET-MA can exist for a long period and
esterification occurs with polyhydroxy compound
PEPAS, which has been used in cotton fabrics32 and
plastic products,33 under the condition of catalysis;
thus, the anti-flame element can be firmly fixed onto
PET and complex and compact net structure can be
effectively constructed. The whole process could be
divided into three stages. Firstly, O-PETs were immersed
in the solution of MA after alkali deweighting treatment,
and then they were air-dried. Secondly, as described in
Figure 1, low-temperature plasma was used to graft MA
onto the macromolecular chain of PET. Finally, PEPAS
was fixed onto the modified PET fabrics by the dip-pad-
ding method and high-temperature chemical finishing.
The fabricated PET fabrics were investigated by
infrared (IR) light, scanning electron microscopy
(SEM) and X-ray photoelectron spectroscopy (XPS)
for chemical structure and microstructure analysis.
Thermogravimetry (TG) and differential thermal ana-
lysis (DTA) were used to analyze thermal stabilities of
the PET fabrics. The characteristics, including the LOI,
durable wash fastness and mechanical stabilities, were
addressed to evaluate the application performance.
Experimental details
Materials
Commercial knitted PET fabrics (weight 184 g/m2) were
kindly provided by Zhangjiagang Helian Textile Co.,
Ltd (Jiangsu, China). Before treatments, the PET fab-
rics were cleaned in an acetone solution under ultra-
sonic condition, and were subsequently washed with
deionized water several times and the dried fabrics
were stored in plastic sealing bags. The alkali deweight-
ing promoter and ECE nonphosphate reference deter-
gent were provided by Yancheng Dyeing and Finishing
Co., Ltd (Jiangsu, China). Absolute alcohol, urea, MA
and sodium hypophosphite were obtained from

HO HO
C O C O
C O

C O
O2 plasma C O C O
O O O
O O
MA HO C CH CH HO C CH CH
CH2 CH2
CH2 H CH2
HO C CH O HO C CH2 O
O
O O

O
OH
O H2C O H3N C NH2
H H2 H2
C C O C C C O P O
PEPAS
CH2 OH HO padding
H2C C OH
OH CH2 NaH2PO2·H2O
O OH O H2 OH
O P O C C C
O C C O H2
OH CH2
H2C CH OH Baking
H2 HO
O CCOC C
H
O O

Figure 1. The proposed mechanism of the flame-retardant finishing for poly(ethylene terephthalate) fabrics.
MA: maleic acid; PEPAS: pentaerythritol phosphate urea salt.
4 Textile Research Journal 0(00)
Shanghai Shengxiang Chemical Reagent Co., Ltd
(Shanghai, China). Pentaerythritol, phosphoric acid,
acetic acid, acetone, paraxylene and sodium hydroxide
were purchased from Sinopharm Chemical Reagent
Co., Ltd (Shanghai, China).
Alkali deweighting treatment
With the liquor ratio of 1:30, the O-PET was soaked in
a solution of 30 g/L NaOH and 5 g/L alkali deweighting
promoter at 80 C for 60 min. After being taken out of
the bath, the fabric was washed with hot deionized
water and soaked in an acetic acid solution to be neu-
tralized, then washed with hot deionized water and cold
deionized water several times until pH neutral. Under
the alkali treatment, PET fiber undergoes hydrolysis
and tapers, resulting in inter-fiber cohesive force being
diminished and gaps, hydrogen bonds, specific surface
areas and the capillary effect being effectively
increased.34 Therefore, the adsorption characteristic
of the PET fabric can be improved. After the
alkali treatment, the weight losses of the PET fabrics
were 11  1%. The alkali deweighting promoter was
a combination of a variety of agents in which
2-pentanol,1,10 ,100 ,1000 -(1,2-ethandiyldinitrilo) tetrakis
was its major component. This promoter can adsorb
on the PET surface to reduce surface tension and cat-
ionic groups in the promoter can absorb hydroxyl ions,
resulting in the abundance on the PET surface, which
can favor completion of the hydrolysis reaction.
Plasma-grafting treatment
A certain amount of MA was dissolved in deionized
water and diluted with deionized water to 5–25%
(mass%). With the liquor ratio of 1:50, the PET
fabric after alkali treatment was immersed in the MA
solution to absorb the MA by the dip-padding tech-
nique at room temperature. Before the plasma treat-
ment, the PET fabric was dried in vacuum drier at
80 C for 30 min. The activation process for the PET
fabric was carried out using a Model HD-1B plasma
instrument (Changzhou Zhongke Changtai Plasma
Technology Co., Ltd, China) with cold oxygen atmos-
phere and at the pressure of 10 Pa. After being treated
at a certain power (50–250 W) for 5 min at an oxygen
gas flow rate of 5 LPM, the plasma-treated fabric
(P-PET) was taken out from the metallic chamber for
the next treatment.
PEPAS synthesis
A total of 13.6 g (0.1 mol) of pentaerythritol and 80 mL
of paraxylene were added into a 250 mL four-necked
flask. After the flask was equipped with a reflux
condenser tube, a water separator and a mechanical
stirrer, 17.2 g (0.176 mol) of phosphoric acid was drop-
wise added into the flask, and subsequently the solution
was well mixed. After heating up to 140 C, the solution
was kept at that temperature until the amount of water
in the water separator stopped rising. Then the reaction
mixture was treated with two different kinds of pro-
cesses: in the first process, the mixture was filtered
while it was hot to remove the solvent and get the
crude product. Then the filter cake was washed thor-
oughly with absolute alcohol and vacuum dried, and a
white powered solid product, pentaerythritol phosphate
(PEPA), could be obtained. In the second process, 22 g
urea was added directly into the reaction mixture and it
was kept at 140 C for 3 h. The mixture was filtered
while hot to get the final product PEPAS and vacuum
dried at 170 C. The reaction mechanism is described in
Figure 2.
Anti-flame finishing treatment
An aqueous solution consisting of PEPAS (100–250 g/
L) and sodium hypophosphite (60 g/L) was prepared
and its pH was adjusted to 3. The P-PET was treated
with the prepared solution by two dipping and two
padding methods at ambient temperature with a pick-
up of 100%. The fabric was subsequently dried at 80 C
for 3 min and cured at 160 C for 3 min in a Model M-6
heat setting machine (Nantong Baolai Textile
Instruments Factory Co., Ltd, China). After this, the
finished PET fabric (F-PET) was washed thoroughly
with water containing 2 g/L Na2CO3 and 2 g/L soap
flakes and cold tap water before being air-dried.
Characterization
The chemical structure of the fabrics (before and after
treatment) and the synthetic anti-flame product were
investigated by Fourier transform infrared spectros-
copy (FT-IR) (Tensor27, Bucker, Germany) with the
attenuated total reflectance (ATR) method at a reso-
lution of 2 cm1 in the range of 650–4000 cm1 and
the KBr squashed method at a resolution of 2cm1 in
the range of 400–4000 cm1, respectively.
The surface morphologies of the fabrics and residual
char from the burning experiments were observed by a
Quanta 200 scanning electron microscope analyzer
(FEI, USA). Elemental analysis was also performed
with a plane scan of energy-dispersive spectroscopy
(EDS). Prior to observation, the PET samples were
sputtered with gold under vacuum.
Surface chemical characterizations of the PET fab-
rics were analyzed with XPS analyses. The XPS experi-
ments were performed on a PHI-5000C ESCA system
(Perkin Elmer, USA) with a mono Al Ka X-ray anode
Zhou et al. 5

OH
H2C OH
H2
H2C C C O P O
H3PO4 O
main product HO OH
H2C OH
H2C O H3N C NH2
OH
CH2OH 140oC o
140 C 3h H2C C O P O

HOH2C C CH2OH urea HO

OH H2C OR
140oC OH
CH2OH H2C OH
H2 OH
by-product H2C C C O P O
CH2
HO H2
H2C O
C C C OH
OH H2
H2C OH

Figure 2. Synthesis processes for pentaerythritol phosphate urea salt.

source (h ¼ 1486.6 eV) at 14.0 kV and 250 W under
ultrahigh vacuum.
Thermogravimetric analysis (TGA) and DTA were
carried out by employing a TG 209 analyzer (Netzsch,
Germany). A total of 5 mg of the PET sample was
loaded into an alumina oxide pan and heated from
25 C to 730 C under air atmosphere at a heating rate
of 10 C min1.
Mechanical properties, such as tensile strength (TS),
elongation at break (Eb) and elasticity modulus (EM),
were examined using a H5K-S universal material test-
ing machine (Hounsfield, England) under the condi-
tions of ambient temperature and 65% relative
humidity at a speed of 12 mm min1 with a 5000 N
sensor loaded.
Anti-flame test
LOI tests were measured on a HC-2C oxygen index
meter (Jiangning Analysis Instrument Company,
China) according to GB/T 5454-1997 (China) with
fabric dimensions of 150 mm  58 mm. The LOI is the
minimum oxygen concentration of an oxygen–nitrogen
mixture that will barely support flaming combustion
under specified practical conditions, and is described
by the oxygen volume percentage.
The vertical burning tests (Underwriter Laboratory
94) were conducted by using a JF-3-type vertical burning
flame-retardant tester (Jiangning Analysis Instrument
Company, China) with a dimensional size of
300 mm  80 mm according to GB/T 5455-1997 (China).
The durability performance of F-PET samples was
subjected to an accelerated domestic laundering
method that was proposed in our previous work.35
Twenty laundry cycles were carried out with the ECE
nonphosphate reference detergent at 40 C. The anti-
flame performance indicators of the fabrics were inves-
tigated after the laundering process.
Results and discussion
FT-IR studies
Figure 3(a) shows the FT-IR spectrum of pentaerythri-
tol and PEPA. As shown in Figure 3(a), it is clear to
observe that the absorption peaks at 3417.56 cm1 of
pentaerythritol and 3334.05 cm1 of PEPA are ascribed
to the stretching vibration of -OH groups. Since the
P¼O bond is successfully introduced into the chemical
structure, the inter-and intra-molecular hydrogen
bonds are effectively enhanced, which leads to shifting
to the low wave number direction and the broadening
of the peaks. The peaks between 2860 and 2960 cm1
arise from the stretching of saturated C-H groups. The
peaks at 1717.06, 1718.78 and 1717.24 cm1 may be
caused by the carbonyl groups of the PET polymer
backbone. Compared to pentaerythritol, the character-
istic peaks centered at 2365.87 and 1234.19 cm1 of the
PEPA correspond to the vibration of P-OHO and
P¼O bonds. These results show that the phosphate
esterification is successfully carried out. Figure 3(b)
shows the FT-IR spectrum of O-PET, P-PET (150 W
and 20% MA) and F-PET (150 W, 250 g/L PEPAS and
20% MA). After plasma treatment, the characteristic
peak centered at 3435.64 cm1 is due to the stretching
vibration of O-H, while there is no corresponding peak
of the pristine PET, which may be caused by the graft-
ing MA and the formation of hydroxyl groups on the
PET polymer backbone. The peaks at 1661.45 and
1548.19 cm1 of F-PET may arise from the stretching
vibration of C¼O and the bending vibration of N-H of
urea. The peak at 1193.74 cm1 may be related to the
P¼O bond, the peak at 971.96 cm1 may be due to the
P-O bond and the stronger peak at 1021.48 cm1 com-
pared with the other two spectra curves may be caused
by the P-O-C bond, indicating that the synthetic anti-
flame agent is successfully incorporated into the polymer
matrix.
6 Textile Research Journal 0(00)

(a) (b) 1548.19 1456.41

971.96
1193.74
1234.19 F-PET 3410.49 2960.68 2858.03 1507.69
PEPA
1637.76 1661.45
2365.87 1021.48
1717.06 1245.53
+
1100.21
1408.39 665.02
2951.90 P-PET 2917.82
T/%

R/%
2873.64 1456.79
3334.05 1015.34 3435.64 1718.78
1020.68
1245.55 1099.03

1633.34 1407.80 2960.25 2854.70

665.01 O-PET 1470.09
1018.77
1408.39
1016.67
pentaerythritol
1339.45
1099.56
1717.24
3417.58 1245.97

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000
-1 -1
Wavenumber / cm Wavenumber / cm

Figure 3. Fourier transform infrared spectroscopy spectra of (a) pentaerythritol phosphate (PEPA), pentaerythritol and
(b) the original poly(ethylene terephthalate) (PET) fabric (P-PET), the plasma-treated fabric (P-PET) and the completely finished PET
fabric (F-PET).

char residues play a vital role in the flame-retardant

Microstructure
Figures 4(a) and (b) present the surface morphology of
O-PET and P-PET, respectively, by SEM. We can see
clearly that the surface morphology of O-PET is
smooth, while that of P-PET becomes obviously
rough, with the appearance of many grooves, fragments
and particles. This can be explained by the PET fibers
being bombarded to increase active groups and the spe-
cific surface area due to the plasma etching effect, which
is beneficial for grafting and adsorbing MA.36 After
treating with PEPAS, we can see that it is successfully
deposited on the surface of PET fibers with heavy dense
embossment and granulated structures, as presented in
Figure 4(c), indicating that MA can firmly fix PEPAS
onto the surface of PET fibers, which results in the
improvement of anti-flame performance.
For studying the solid phase flame retardancy, the
inner surface morphologies of char residues of O-PET
and F-PET are shown in Figures 4(d)–(f). From these
SEM images, we can observe clearly that lots of bub-
bles and large holes spread all over the inner surface
(Figure 4(d)), which can transfer heat and diffuse fuel
gas to aid the flame. However, Figures 4(e) and (f) show
that the compact and intact char microstructures and
the surface of char residues of F-PET are showing
roughness and are covered with a uniformly distributed
high density of substances. These specific compact
micro substances form a barrier that can effectively
provide the heat insulation and protect the PET
matrix from contacting fire, as well as inhibit smoke,
to achieve good anti-flame performance and non-
dripping effects. Since the element composition of
performance, the energy-dispersive X-ray spectroscopy
(EDXS) map analyses of char residues are shown in
Figure 5. It reveals that the introduced phosphorus
and nitrogen retardant elements are successfully depos-
ited on the surface of the char residues.
Thermal stability
The thermal behaviors under air atmosphere of O-PET
and F-PET samples were investigated by TGA, as
shown in Figure 6. From Figure 6(a), both samples
exhibit two major thermal degradation stages and
F-PET begins to degrade at a lower temperature than
O-PET because of the decomposition of PEPAS, which
can release active ingredients to inhibit combustion.
The first stage corresponds to the degradation of the
polymer main chain, while the second stage arises from
a further oxidative process. It can also be easily visua-
lized that the weight loss curve of O-PET drops more
dramatically than that of F-PET, indicating that the
latter has a relatively small heat generation rate. The
percentage of remaining residues of O-PET is 0.164%,
while that of F-PET is 6.004% at 730 C.
From Figure 6(b), for the maximum decomposition
rate temperature (Tmax) of the first stage, there is little
difference between O-PET (455.33 C) and F-PET
(453.48 C). However, the peak at the second stage
can be improved from 515.68 C to 555.40 C after
plasma and anti-flame treatment, which is attributed
to the formation of dense char layers and the stable
cross-linking networks. Cross-linking can be formed
between two polymer main chains, since the synthetic
Zhou et al. 7

Figure 4. Surface scanning electron microscopy pictures of (a) original PET fabric (O-PET), (b) plasma-treated fabric, (c) finished PET
fabric (F-PET), (d) char residues of O-PET and (e) and (f) char residues of F-PET.
PET: poly(ethylene terephthalate).

Figure 5. The energy-dispersive X-ray spectroscopy map analyses of the char residues of finished poly(ethylene terephthalate) fabric.
8 Textile Research Journal 0(00)

transition and melting behaviors, while the two

(a)
100
decomposition exothermic peaks of the two curves
changed significantly. Compared with O-PET, F-PET
80 not only shows smaller intensity but also has a later
exothermal temperature range, which indicates that
the anti-flame treatment could reduce the total heat
Weight / %

60

release, promote the formation of char and improve

40 the anti-dripping property.
F-PET
20

O-PET
XPS analysis
0
To further investigate the relationship between the
0 100 200 300 400 500 600 700 800 chemical structure and flame retardance, XPS spectra
o
Temperature / C were studied on the fire residues of the LOI test. As
(b)
shown in Figure 7(a), it is clearly seen that the fire resi-
O-PET dues of F-PET mainly contain C (C1s, 284.4 eV),
O (O1s, 532.7 eV), N (N1s, 400.1 eV) and P (P2p,
134.1 eV) elements, while those of O-PET mainly con-
-1

tain C (C1s 284.6 eV) and O (C1s 533.1 eV) elements.

DTG / mg min

These data are in accordance with others reported in

the literature.22,37,38 After treatment, the relative con-
F-PET
tent of C1s decreased from 76.17% (that of O-PET) to
71.29%, while O1s increased from 21.26% (that of
O-PET) to 22.05%, and the relative contents of P2p
and N1s were 2.42% and 4.24%, respectively. The
0 100 200 300 400 500 600 700 800 XPS deconvolution scans for the P2p spectra of
o
Temperature / C F-PET are shown in Figure 7(b), and the binding
(c) energy peaks centered at 133.40 and 134.25 eV corres-
200 pond to P-O and P¼O,39 indicating that phosphorous
compounds, such as P2O5 and phosphate ester, are
150 formed due to the oxidation and pyrolysis process.40
O-PET
According to the above analysis, it can be confidently
DTA / uV

100
concluded that the existence of phosphorous and nitro-
F-PET gen, by the synergistic effect, can effectively promote
the formation of a stable carbon layer, extinguish
50
flames and inhibit dripping for PET fabrics.

0
0 100 200 300 400
Temperature / C
Figure 6. (a) The thermogravimetry analysis. (b) The derivative
thermogravimetric analysis (DTG). (c) The differential thermal
analysis (DTA) of the original PET fabric (O-PET) and finished
PET fabric (F-PET).
PET: poly(ethylene terephthalate).
anti-flame agent includes at least two active groups.
Furthermore, the height of the peak in O-PET is
higher than that of F-PET, indicating that grafting
PEPAS can effectively retard drastic decomposition.
DTA is also adopted to evaluate the burning behaviors
of O-PET and F-PET, and the data is displayed in
Figure 6(c). The two curves show similar glass
Mechanical properties
500 600 700 800
o
The typical stress–strain curves of O-PET, PET after
the alkali bath and F-PET are presented in Figure 8.
The average tensile stress at break of O-PET, PET after
the alkali bath and F-PET are 14.40, 11.54 and
15.23 MPa, respectively; the values for Eb are
119.40%, 102.53% and 77.61%, respectively; and the
modulus elasticity values are 12.73, 15.17 and
30.99 MPa, respectively. All three types of samples dis-
play soft and flexibility features and have excellent
mechanical properties, which indicates the treatment
has had little adverse impact on the bulk of the PET
fabrics. After alkali deweighting treatment, tensile
stress at break and Eb show a trend of decline, which
may be mainly caused by the degradation effects of
PET under alkali conditions. However, we are inter-
ested in finding whether the TS has a certain
Zhou et al. 9

(a) (b)

C1S
P-O 133.40
O1S
134.25 P=O

the final PET fabric

N1S

P2P

the neat PET fabric

0 600 1200 128 130 132 134 136 138 140 142
Binding Energy (eV) Binding energy (eV)

Figure 7. X-ray photoelectron spectroscopy survey scan spectra of fire char for original PET fabric (O-PET) and finished PET fabric
(F-PET).
PET: poly(ethylene terephthalate).

Flame retardancy
120 The flame retardancy of the PET fabrics was firstly
evaluated by the LOI, and a single factor analysis of
100 the flame-retardant finishing process was carried out.
The corresponding experimental data are listed in
80 F-PET
Tensile force / N

60
40
20
0 monomer molecules are successfully introduced onto
0 20 40
Displacement / mm
Figure 8. Stress–strain curves of original PET fabric (O-PET),
poly(ethylene terephthalate) (PET) after the alkali bath and fin-
ished PET fabric (F-PET).
improvement instead of decreasing after the anti-flame
treatment. Although the plasma and alkaline treat-
ments cause a negative effect on the mechanical
properties, the cross-linking effects, hydrogen bonds
and inter-molecular forces between the modified PET
macromolecules can effectively enhance the tensile
stress at break. Yet, it is this enhancement that inhibits
the slip ability of PET macromolecules and the Eb
decreases significantly. In addition, the baking steps
of the finishing process may result in recrystallization
behaviors, which may be partly responsible for the
improvement of tensile stress at break.
Table 1.
O-PET
It is shown that the LOI value increases with the
increase in plasma power density at first, but if the
power continues to increase, the LOI values show a
descending tendency. A proper increase of plasma
PET after alkali
deweighting
power can generate more free radicals, which results
treatment in an improved grafting degree and thus more MA
60 80 100
the surface of PET fabrics and frequently react with
PEPAS to form strong covalent bonds. After the
power density exceeds 150 W, the polymerization of
MA itself is enhanced, while the grafting between MA
and PET macromolecule decreases, which leads to the
decline in the covalent bonds between PEPAS mol-
ecules and PET macromolecules. On the other hand,
if the power density is too high, the surfaces of the
plasma-treated PET fabrics will be seriously etched
and their weave structures will be loosened and
damaged to a certain extent, and then the contacting
part with oxygen will be enhanced during the combus-
tion, which has a negative impact on the anti-flame
effect. With the consideration of each performance of
various plasma power densities, the optimum value is
150 W.
As shown in Table 1, PEPAS was added in the
amount of 100–300 g/L to the anti-flame finishing solu-
tion, and we found that the LOI value increased to 29.1
when the concentration of PEPAS reached 250 g/L,
then even if more PEPAS was added into the solution,
10 Textile Research Journal 0(00)

Table 1. Single factor analysis of the effect on the limiting PEPAS cannot be well bonded with the modified PET
oxygen index (LOI) under the condition of adjusting plasma macromolecules due to the limited active sites.
power, the amount of maleic acid (MA) and the amount of pen- Therefore, no obvious enhancement of the LOI was
taerythritol phosphate urea salt (PEPAS) found by further increasing the amount of PEPAS;
Sample Plasma The amount The amount thus, 250 g/L was chosen as the optimum amount of
number power (W) of MA (%) of PEPAS (g/L) LOI PEPAS.
From the data listed in Table 1, the LOI value
0 – – – 20.2  0.16
increases from 24.6 to 29.1 with the concentration of
1 50 20% 250 25.7  0.32
MA adjusted from 5% to 20%. Subsequently, the LOI
2 100 20% 250 28.0  0.64
value tends to slightly decline when the concentration
3 150 20% 250 29.1  0.31
of MA reaches 25%. By increasing the concentration of
4 200 20% 250 28.4  0.23
MA after alkali deweighting treatment, the amount of
5 250 20% 250 27.7  0.45
MA on the PET fabric increases by adsorption.
6 150 20% 100 23.4  0.50
Therefore, more active sites can be generated corres-
7 150 20% 150 25.6  0.35
pondingly, which effectively improve the reaction with
8 150 20% 200 27.1  0.35
PEPAS. However, the growth reduces gradually due to
9 150 20% 300 29.3  0.29
the saturation of the adsorption capacity. Furthermore,
10 150 5% 250 24.6  0.45
an excessive amount of MA also enhances the chances
11 150 10% 250 25.5  0.29
of self polymerization and weakens the combination of
12 150 15% 250 27.9  0.40
MA and PET, which results in the slightly declined
13 150 25% 250 28.6  0.40
LOI.
Note: plasma 5 min, curing temperature 160 C, curing time 3 min, According to the above analysis, the technical par-
sodium hypophosphite 60 g/L, penetrating agent 2 g/L, pH ¼ 3. ameters of anti-flame finishing were determined: MA
20%, PEPAS 250 g/L, pH ¼ 3, sodium hypophosphite
there were no significant changes in the LOI. PEPAS 60 g/L, penetrating agent 2 g/L, power density 150 W,
could improve the anti-flame properties of PET in two plasma time 5 min, curing temperature 160 C, curing
ways. On the one hand, it can generate PO to capture time 3 min. Then the optimal treated fabrics were
H, which effectively interrupts the exothermic process tested by the LOI and vertical burning test, and the
and inhibits combustion, but this is just a minor aspect. results are listed in Table 2. After ignition, the
On the other hand, it can change the thermal cracking O-PETs could not self-extinguish and almost burnt
process of PET and is beneficial to the formation of the out, with obvious melts dripping away from the flaming
char layer and water; thus, the amount of combustible fabrics. The treated PET samples could reach
gas is greatly decreased. The latter is the major aspect. UL-94 V-0 grade and the flame almost instantly went
Furthermore, PEPAS is an integrated organophos- out after removing the igniter, showing an excellent
phorus intumescent fire-proofing agent. The phos- anti-flame performance and self-extinguishing prop-
phorus element removes water and displays erty. Neither type of sample showed a smoldering phe-
condensed phase flame retardation to promote the for- nomenon. During the UL-94 flame test for the treated
mation of the carbon layer. N2 and NH3, which are samples, the absorbent cotton could not be ignited,
derived from the nitrogen element in PEPAS, can which demonstrated that the melt dripping property
dilute the flammability of the gas and result in foaming was suppressed successfully. The excellent anti-dripping
and intumescing phenomena to form a highly dense effect may be attributed to the cross-linking behavior,
and micro-porous fire-proofing char layer. Integrating which can increase the melt viscosity and reduce the
phosphorus and nitrogen into an anti-flame-retardant flowability.41 Moreover, when the treated PET fabrics
agent, they can create synergistic effect with each other burnt, the three-dimensional cross-linking system acted
and greatly improve the efficiency of the flame retard- as a net in which the molten droplets could be encased,
ant.26 The pentaerythritol component acts as a carbon and thus prevent dripping.42 Furthermore, esterifica-
source and is the foundation of the foam char layer. tion, dehydration, expanding and cross-linking occur
Moreover, a PEPAS molecule can simultaneously form during the heating process for the treated samples,
more than two covalent bonds with different modified which results in the formation of foaming and an intu-
PET macromolecules due to having several hydroxyl mescing char layer on the surface of the PET matrix.
groups in the structure, so it can be firmly combined The char layer can effectively inhibit the thermal
with the PET matrix and the TS of the treated PET decomposition of the interior PET matrix and decrease
fabric can be effectively improved, which has been the amount of combustible gas, subsequently decreas-
proved in the mechanical test. As the grafting degree ing the heat of combustion and the heat release rate.
of MA is determined by the previous process, too much Therefore, the formation of molten droplets becomes
Zhou et al.
Table 2. The limiting oxygen index (LOI) and vertical flame test of original PET fabric (O-PET), finished PET fabric (F-PET) and F-PET
after laundering 20 times
Sample LOI (%) UL-94
O-PET 20.2  0.16 V-2
F-PET 29.3  0.29 V-0
F-PET after laundering 26.8  0.42 V-0
PET: poly(ethylene terephthalate).
relatively difficult. In order to evaluate the durability of
the anti-flame agent to washing, the treated samples
were investigated by the accelerated laundering
method (20 times of domestic laundering). From the
data listed in Table 2, the LOI value declines from
29.3 to 26.8. This may be caused by the ablation
of PEPAS in the washing process. Compared with
O-PET fabric, which has LOI ¼ 20.2, F-PET shows a
durability in the flame-retarding effect, and this sug-
gests that PEPAS can be firmly combined with the
PET fabric. The LOI values of the treated fabrics are
comparable to those of P(ET-co-BP)x (25.9–29.2),43
BAnPETs (22.0–31.0),3 BDxPET (28.4)44 and
sPMCMSs/PET (25.5–27.2)45 and higher than those
of AxPET and FxPET (23.3–26.0),46 GMA-g-PET/FR
(25.9)8 and PET-g-PGMA/DVB (21.5),47 but still much
lower than those of PET/AF (35.3),48 PET/HNCP/
POE-g-MA (26.8–35.1)1 and PAN/PET (42.0),36 so
many aspects, such as the catalyst composition,
plasma atmosphere and gas flow rate, need to be
researched to get further improvements in the anti-
flame performance of PET fabrics.
Conclusions
Herein, a plasma-based method is reported to achieve a
durable anti-flame effect for polyester fabrics. Alkali
deweighting treatment can effectively destroy the sur-
face compactness of PET and enlarge the specific sur-
face area to absorb more MA, which can form a bridge
between PET and PEPAS. The plasma-induced PET-
MA can exist for a long period and esterification with
polyhydroxy compounds and PEPAS occurs under the
condition of catalysis; thus, the anti-flame element can
be firmly fixed onto PET and the complex and compact
net structure can be effectively constructed. The opti-
mal anti-flame finishing process conditions were MA
20%, PEPAS 250 g/L, pH ¼ 3, sodium hypophosphite
60 g/L, penetrating agent 2 g/L, power density 150 W,
plasma time 5 min, curing temperature 160 C, curing
time 3 min. Under optimum formulation, the LOI
11
Vertical burning test
Melt Molten droplets Ignition
dripping within 10 s cotton
heavy 8 Yes
none 0 (self-extinguish) No
little 3 (self-extinguish) No
value of the treated sample reached 29.3 and showed
better anti-dripping performance than that of the
untreated sample. The results of characterization with
FT-IR, EDS and XPS showed that MA and PEPAS
were successfully introduced onto the surface of the
PET fibers. From the SEM, it could be seen that the
dense char layer formed at high temperature was
enhanced obviously due to the firm coverage of the
anti-flame agent. Compared with the O-PETs, the TSs
and thermal stabilities of the treated fabrics exhibited
significant improvement. In the vertically burning test,
the treated fabrics could achieve a self-extinguishing
effect, while the untreated samples almost burnt out.
Moreover, the cross-linking structure formed between
PEPAS and PET could impart good anti-dripping per-
formance. After 20 laundering cycles, the LOI value of
the treated sample remained at 26.8 and the treated
sample still reached the UL-94 V-0 grade, which
meant a good laundering durability. This modification
method might provide a novel, environmental way to
improve the flame retardancy of polyester fabrics as
well as good laundering durability.
Acknowledgments
Many thanks to Yancheng Dyeing and Printing Co., Ltd, for
generously providing some of the chemicals.
Declaration of conflicting interests
The authors declared no potential conflicts of interest with
respect to the research, authorship and/or publication of this
article.
Funding
The authors disclosed receipt of the following financial support
for the research, authorship, and/or publication of this article:
This work was supported by the Science Project of the China
Textile Industry Federation (Project Number: 2015021), the
Open Foundation of the Provincial Research Platform of
Yancheng Vocational Institute of Industry Technology (Project
Number: YGKF-201707) and the National Natural Youth
Science Foundation of China (Project Number: 51803175).
12
ORCID iD
Tianchi Zhou https://orcid.org/0000-0002-6530-9629
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