Polymer Degradation and Stability 172 (2020) 109064

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Polymer Degradation and Stability

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

Synthesis of organophosphate-functionalized graphene oxide for

enhancing the flame retardancy and smoke suppression properties of
transparent fire-retardant coatings
Long Yan*, Zhisheng Xu, Nan Deng
Institute of Disaster Prevention Science and Safety Technology, School of Civil Engineering, Central South University, Changsha, 410075, China

a r t i c l e i n f o a b s t r a c t

Article history: A series of organophosphate-functionalized graphene oxide flame retardants (GPPBs) were successfully
Received 11 August 2019 synthesized by grafting flexible phosphate ester (PPB) on the surface of graphene oxide (GO), and well
Received in revised form characterized by Fourier transform infrared (FTIR) spectroscopy and 1H nuclear magnetic resonance (1H
21 November 2019
NMR) spectroscopy. The obtained GPPBs were then incorporated into amino resin to produce transparent
Accepted 30 December 2019
fire-retardant coatings for reducing the fire hazard of wood. The transparency analysis shows that the
Available online 2 January 2020
GPPBs endow the resulting coatings with a high degree of transparency even at a relatively high GO
contents due to the uniform dispersion and completely exfoliated states of GO in amino matrix. The
Keywords:
Functionalized graphene oxide
evaluation of combustion behavior reveals that the introduction of GO greatly reduces the weight loss,
Flexible phosphate ester char index, flame spread rating (FSR), smoke production and heat release of the coatings concomitant
Flame retardancy with an increase in the insulation property, for example, 60.7% reduction in smoke density rating (SDR)
Smoke suppression and 33.3% reduction in total heat release (THR) are observed in the case of MGPPB3 coating obtained
Transparent fire-retardant coating from GPPB3 with 0.07 wt% GO in comparison to MGPPB0 coating obtained from PPB. Thermo-gravimetric
analysis shows that the thermal stability and residual weight of the coatings are improved after intro-
duction of GO, and MGPPB3 exhibits the highest residual weight of 34.5% at 700
C. The main mechanism
of the GPPBs for enhancing the fire safety of transparent fire-retardant coatings is ascribed to the for-
mation of high-quality intumescent char with excellent compactness, anti-oxidation ability and barrier
effect against fire.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
Wood is widely applied as building and decoration materials
due to its excellent mechanical properties, low cost, and unique
aesthetic characteristics [1]. However, the inherent flammability of
wood restricts its practical application in many fields with high fire
safety requirements especially in densely populated areas. To
eliminate this potential fire hazard, the deposition or impregnation
of flame-retarded additives has been widely applied to enhance the
fire safety of wood and wood-based materials [2,3]. Inorganic salts
such as borates, phosphates, silicates and potassium carbonates, are
widely utilized to reduce the flammability of wood by a simple
* Corresponding author. Institute of Disaster Prevention Science and Safety
Technology, Railway Campus, Central South University, 22 South Shaoshan Road,
Changsha, 410075, China.
E-mail address: ylong015@csu.edu.cn (L. Yan).
impregnation process due to their low cost and high flame-
retardant efficiency [4]. However, the cost and energy-intensive
drying process brings a potential problem for large-scale indus-
trial application of the impregnated wood.
The application of inorganic or organic coatings is an effective
and simple approach to protect the wood from the threat of fire
[5,6]. Compared to opaque coatings, transparent coatings are
appreciated widely in some fields such as cultural relics, heritage
conservations and high-quality furniture [7,8]. Especially, trans-
parent intumescent fire-retardant coating is one of attractive
transparent coatings and possesses satisfactory applications in
wood and wood-based products due to its excellent hydrophobic-
ity, decorative property and fire protection performance [9,10]. It is
well known that transparent intumescent coatings are usually
produced by physical blending phosphate esters with amino resin
[11,12]. When exposed to heat or flame, phosphate esters can
capture OH$ and H$ radicals in the gas phase by releasing PeO$
radicals and catalyze the carbonation of carbon-rich components in

https://doi.org/10.1016/j.polymdegradstab.2019.109064
0141-3910/© 2020 Elsevier Ltd. All rights reserved.
2 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064
the condensed phase by releasing inorganic acid, thus effectively
reducing the combustion intensity [13]. Meanwhile, amino resin
produces incombustible gases (NH3 and H2O) to dilute the oxygen
in the combustion zone and promote the intumescence of the
molten char. However, most of those kinds of amino transparent
coatings have a relatively low flame-retardant efficiency. To
improve the flame-retardant and smoke suppression efficiencies of
amino transparent intumescent coatings, some synergistic ele-
ments containing boron, silicon, aluminum and magnesium are
introduced into phosphate esters [14e16]. In addition, the incor-
poration of nano-fillers as synergists exhibits enormous potential
to enhance the flame retardancy and smoke suppression properties
of transparent fire-retardant coatings, and these nano-fillers
include nano-silica [17], organically modified montmorillonite
[18], polyhedral oligomeric silsesquioxane (POSS) [19].
Graphene oxide (GO) as the precursor of graphene with a two-
dimensional layered structure and rich functional groups that
could be easily functionalized by flame-retardant compounds or
polymers [20]. GO has superior thermal property and barrier effect
that make itself promising application in the field of flame-retarded
materials [21]. However, the van der Waals forces between the
graphene sheets result severe agglomeration inclination of GO in
polymer matrix, which induce significant light scattering and thus
restrict its application in transparent materials [22,23]. To solve this
problem, many efforts have focused on the functionalization of GO
with flame retardants containing phosphorus, nitrogen and/or sil-
icon elements to obtain uniform dispersion of GO sheets in polymer
matrix. Shi [24] and Ran [25] et al. reported on the decorating GO
with P, N-containing flame retardants for acquiring well dispersion
of GO and superior flame retardancy and smoke suppression
properties of polymer materials. Bao et al. found that the intro-
duction of N and P elements on the surface of GO results in compact
and continuous char to protect the underlying materials against the
fire, and the enhanced char can greatly improve the fire safety of
polymeric materials [26]. Wang et al. grafted silicon-phosphorus
flame retardant (DOPO-VTES) on the surface of GO to synthesis
functionalized graphene oxide (DV-GO), and found that the DV-GO
can be applied to develop high performance resins with excellent
flame retardancy [27]. Thus, it is anticipated that functionalized GO
with phosphate esters could provide superior flame retardancy and
smoke suppression properties to amino transparent fire-retardant
coatings concomitant with a high degree of transparency. Howev-
er, the influence of functionalized GO on the optical transparency,
flame retardancy and smoke suppression properties of transparent
fire-retardant coatings has been rarely investigated.
In this work, a flexible phosphate ester (PPB) was grafted on the
surface of GO to obtain a series of organophosphate-functionalized
GO flame retardants (GPPBs), and well characterized by FTIR and 1H
NMR spectra. Then, the obtained GPPBs were added into amino
resin to produce transparent fire-retardant coatings. The influence
of GPPBs on the optical transparency, mechanical properties, fire
protection performance and smoke suppression properties of the
coatings was investigated by various analytical methods, and the
potential flame-retardant and smoke suppression mechanism of
the GPPBs in the coatings was also proposed.
2. Experimental
2.1. Materials
Graphite oxide (mass fraction of C element: 47 ± 5%, molar ratio
of C/O: 0.6 ± 0.1) was provided by the Sixth Element (Changzhou)
Materials Technology Co., Ltd (Changzhou, China). Polyethylene
glycol with molecular weight of 200 (PEG200) and n-butyl alcohol
(n-BA) were acquired from Sinopharm Chemical Reagent Co., Ltd.,
Shanghai, China. Boric acid (BA, purity: 99.5%) and phosphoric acid
(PA, 85.0% in water) were acquired from Hunan Huizhong Chemical
Reagent Co., Ltd. (Changsha, China). Pentaerythritol (PER, purity:
99.5%) was acquired from Hangzhou JLS Flame Retardant Co., Ltd.,
China. Melamine formaldehyde resin (MF, model 303e80, 58e62%
in n-BA) was provided by Jiyang Sanqiang Chemical Reagent Co.,
Ltd. (Shandong, China). All the above reagents were used as
received without further purification.
2.2. Synthesis of PPB and the GPPBs
Flexible phosphate ester (PPB) was synthesized by the esterifi-
cation of cyclic phosphate ester (PEA) and polyethylene glycol
borate (PEG-BA) with a mass ratio of 85:15 according to the pro-
cedure as reported [16]. In the first step, the mixture of PA
(138.4 g,1.2 mol), PER (46.3 g, 0.34 mol), and n-BA (14.8 g, 0.2 mol)
was added into a 500-mL three-neck flask, and then magnetically
stirred under refluxing for 4 h at 105
C in an oil bath. Afterwards,
the transparent liquid named PEA was obtained by cooling and
removing water under reduced pressure distillation. In the second
step, PEG200 (0.3 mol, 60 g) and BA (6.2 mol) were added into a
500 ml three-necked flask with magnetic stirring at 130
C for 3 h.
After the reaction finished, the yellow transparent liquid named
polyethylene glycol borate (PEG-BA) was obtained by cooling and
removing the water under reduced pressure distillation. In the
third step, 85 g PEA and 15 g PEG-BA were added to a 500-mL three-
necked flask with magnetic stirring under 50
C for 1 h, then the
temperature raised to 115
C for refluxing 4 h. Finally, a transparent
liquid named PPB was obtained by distillation under reduced
pressure for removing the water.
The above PPB was grafted on the surface of GO to obtain a series
of organophosphate-functionalized graphene oxide flame re-
tardants (GPPBs) via a two-step process, as shown in Scheme 1. In
the first step, 0.5 g graphene oxide was dispersed in 500 mL
deionized water by ultrasonication under 50
C for 1 h, and then
the above homogenous suspension was filtrated and dried at 60
C
for 24 h to obtain graphene oxide (GO). In the second step, an
excessive content of PPB was reacted with GO to remain a relatively
high acid number that can promote the ambient-temperature
curing of the amino resin. Briefly, the mixtures of GO and PPB at
different mass ratios (i.e., 99.97:0.03, 99.95:0.05, 99.93:0.07, and
99.9:0.1) were added in a 500-mL three-necked flask with mag-
netic stirring at 50
C for 1 h, then stirred under 90
C for 6 h to
obtain liquid product. The liquid product was distilled under
reduced pressure to remove water, then a series of homogenous
liquid was obtained and designated as GPPBs. The theoretical
loading of GO in the GPPBs and the acid number values of the GPPBs
are listed in Table 1, and the acid number values of the GPPBs were
tested according to ASTM D664-11a (2017).
2.3. Preparation of transparent fire-retardant coatings
The preparation procedure of transparent fire-retardant coat-
ings is shown in Fig. 1. The coating liquid was obtained by mixing
50 g PPB or GPPBs ethanol solution (60 wt%) and 60 g MF n-butyl
alcohol solution (58e62 wt%). The coating liquid was then coated
on the plywood boards (75 mm  75 mm  4 mm,
100 mm  100 mm  4 mm, 150 mm  150 mm  4 mm and
600 mm  90 mm  4 mm) in an amount of 500 g/m2, and the
thickness of dry film reached to 0.4 mm ± 0.02 mm. The coating
liquid coated on the plywood boards with dimension of
300 mm  150 mm  4 mm in an amount of 250 g/m2, and the
coatings were cured to 0.2 mm ± 0.02 mm thick film. The coatings
obtained from PPB and GPPB1-GPPB4 were designated as MGPPB0
and MGPPB1-MGPPB4, respectively.
 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064 3

Scheme 1. Synthesis route of the GPPBs flame retardants.

Table 1 Optical transparency of the fire-retardant coatings was

The composition and acid number values of PPB and the GPPBs. measured using an LS116-type light transmittance meter (Shenz-
Samples PPB GPPB1 GPPB2 GPPB3 GPPB4 hen Linshang Technology Co. Ltd, China). All the films were coated
on a transparent glass slide with a thickness of 0.2 ± 0.02 mm. Five
Acid number (mg KOH/g) 298.9 ± 5 265.8 ± 4 247.5 ± 4 226.8 ± 5 202.2 ± 5
w (GO)/wt% 0 0.03 0.05 0.07 0.1 runs were repeated for each sample and the average value was
recorded.
X-ray diffraction (XRD) patterns were collected on a D/MAS-YA
2.4. Measurements and characterization X-ray diffractometer (Rigaku, Japan), using a Cu-Ka radiation
(a ¼ 0.1542 nm) range from 5
to 40
at a scanning rate of 2
/min.
Fourier transform infrared (FTIR) spectra were recorded on a Optical digital images of the coatings applied on wood sub-
Nicolet FTIR IS5 spectrometer (Nicolet Instrument Co., USA) using a strates were observed by using a VHX-6000 3D optical digital mi-
KBr pellet in the range of 4000e500 cm1. croscope (Keyence, Japan).
1
H nuclear magnetic resonance (1H NMR) spectra were obtained The hardness of the coatings was measured by pencil test ac-
on a Bruker Ascend 500 MHz NMR spectrometer (Bruker, cording to ISO 15184e2012. The adhesion property of the coatings
Switzerland), using D2O as solvent. was analyzed by tape test according to ASTM D3359-09. In the
pencil and tape tests, the coatings with the thickness of

Fig. 1. Preparation process of the transparent fire-retardant coatings on wood substrates.

4 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064
Fig. 2. FTIR spectra of GO, PPB and GPPB3.
0.4 mm ± 0.02 mm were applied on plywood boards under test, and
finial values of the test were the average of five determinations.
Scanning electron microscope (SEM) images were acquired on a
MIRA 3 LMU scanning electron microscopy (Tescan, Czech Repub-
lic) under a voltage of 20 kV. Energy dispersive X-ray spectroscopy
(EDS) maps were conducted on an X-Max20 X-ray probe (Oxford
instruments, UK) for elemental analysis.
Cabinet method test was conducted using an XSF-1-type fire-
resistant paint tester (small room mode) (Jiangning Analysis In-
strument Company, China) according to GB12441-2018 and ASTM
D1360-2011, and the dimensions of each specimen was
300  150  4 mm3. The final values of the test were the average of
Fig. 3. 1H NMR spectra of PPB and GPPB3 flame retardants.
five determinations.
Tunnel method test was carried on a SDF-2-type 2-foot flame
tunnel instrument (Jiangning Analysis Instrument Company, China)
according to ASTM D3806-2011, and the dimensions of specimens
were 600  90  4 mm3. The final flame spread rating (FSR) values
of the test were the average of five determinations.
The heat insulation properties of the coatings were examined by
a small scale “big panel method” test, and the coated side of
specimens was exposed to a Bunsen burner that offered an
approximately 900
C high-temperature flame. The dimension of
specimens was 150 mm  150 mm  4 mm.
Smoke density test was carried on a smoke density test machine
(PX-07-008, Suzhou Phinix Analysis Instrument Co. Ltd, China)
according to ASTM D 2843e99. The coated side of specimen was
exposed to the propane burner, and the dimensions of each spec-
imen were 75 mm  75 mm  4 mm.
Cone calorimeter test was conducted to record the heat release
of the coatings according to ISO5660-2002 (FTT, UK) under an
external heat flux of 50 kW/m2. The size of the specimen was
100 mm  100 mm  4 mm, and the side of the specimen with
coatings was horizontally exposed to the heat radiator.
Thermogravimetric (TG) analysis was performed on a SOTA-851
(Mettler-Toledo, Switzerland) instrument with a heating rate of
10
C/min under a nitrogen flow of 40 mL/min.
X-ray photoelectron spectroscopy (XPS) was measured on an
ESCALAB250Xi electron spectrometer (ThermoFisher-VG Scientific,
USA). The energy step sizes for XPS survey spectra and sole element
XPS spectra were selected as 1.0 eV and 0.05 eV, respectively.
3. Results and discussion
3.1. Characterization of the GPPBs flame retardants
The FTIR spectra of GO, PPB and GPPB3 are shown in Fig. 2. In the
 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064 5

Fig. 4. Digital photos of the flame retardants and their resulting transparent coatings applied on wood substrates.

spectrum of GO, the peaks at 3448, 2921, 1638, 1404, and 1110 cm1
are assigned to the stretching vibration of eOH, CeH, CeO in COOH,
CeOH and CeOeC, respectively [28,29], indicating GO has CeOH
groups that provide the ability to synthesize GPPBs flame re-
tardants. In the spectrum of PPB, the peaks at 2361, 1638, 1466,
1352, 1119, 991 and 885 cm1 are assigned to CeH stretch vibration,
eOH bending vibration, eCH2 deformation vibration, BeOeC
stretch vibration, CeOeC stretch vibration, exocyclic PeOeC
stretch vibration, and cyclic PeOeC stretch vibration, respectively
[16], revealing the successful synthesis of PPB in Scheme 1. After the
functionalization of GO by PPB, the majority of characteristic peaks
appeared in the spectra of both GO and PPB are found in the
spectrum of GPPB3, confirming that PPB was successfully grafted
on the surface of GO.
The chemical structures of PPB and GPPB3 are further confirmed
by 1H NMR spectra, as presented in Fig. 3. In the spectrum of PPB,
two major signals in 3.16e3.27 ppm and 4.81 ppm are assigned to
the H atoms adjacent to exocyclic PeOeC groups (labeled 3) and
the H atoms adjacent to cyclic PeOeC groups (labeled 4 and 5),
respectively. The peaks at 0.46 ppm and 0.90e1.22 ppm are
assigned to the H atoms in the structure of n-BA (labeled 1) and
PEG-BA (labeled 2), respectively. When GO is introduced, the major
peaks of exocyclic H atoms (labeled 3) and the H atoms in n-BA
(labeled 1) and PEG-BA (labeled 2) in the spectrum of GPPB3 exhibit
lower frequency than those of PPB due to the anisotropy of protons
in olefin structures of GO. In addition, the cyclic H atoms (labeled 4
and 5) move to high frequency of 4.93 ppm in the spectrum of
GPPB3 from 4.81 ppm in the spectrum of PPB due to the increase of
electronegativity after introduction of PeOeC groups adjacent to
GO. The above results confirm that PPB was successfully grafted on
the surface of GO to prepare GPPBs flame retardants as shown in
Scheme1.
3.2. Optical transparency analysis
The digital photos of the flame retardants and their resulting
transparent coatings applied on wood substrates are shown in
Fig. 4. It can be found that the transparency of the GPPBs gradually

Fig. 5. SEM images of the fractured surfaces of MGPPB3 coating magnified at 500 and 2000 times.
6 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064

Table 2
Hardness and adhesion properties of the transparent coatings.

Samples MGPPB0 MGPPB1 MGPPB2 MGPPB3 MGPPB4

Pencil hardness 3B 3B 3B 2B 2B
Adhesion classification 4B 4B 3B 2B 3B

Table 3
Fire protection performance of the samples assessed by the cabinet method and
tunnel method tests.

Samples Uncoated MGPPB0 MGPPB1 MGPPB2 MGPPB3 MGPPB4

Weight loss (g) 15.5 ± 0.6 3.2 ± 0.5 3.0 ± 0.3 2.8 ± 0.3 2.3 ± 0.1 2.5 ± 0.1
Char index (cm3) 35.6 ± 3.2 11.3 ± 0.6 9.1 ± 2.1 8.4 ± 0.2 3.3 ± 0.5 6.4 ± 1.2
FSR 66.2 ± 4 17.5 ± 3 12.7 ± 2 10.7 ± 1 6.9 ± 1 8.7 ± 1
Intumescent 0 35.5 ± 5 48.0 ± 4 63.5 ± 5 90.5 ± 4 71.3 ± 5
factor

Fig. 6. XRD patterns of GO and the resulting transparent coatings.

decreases with increasing GO content, and GPPB4 forms a black and
uniform liquid without phase separation, as viewed by naked eyes.
The uniform distribution of GO in the GPPBs helps to endow the
resulting coatings with a high degree of transparency. From the
appearance of MGPPBs coatings, it can be seen that the trans-
parency value of MGPPBs is gradually decreased with increasing GO
loading, which is ascribed to the light scattering of GO hampers the
transmission of visible light and then decreases the level of trans-
parency. In detail, MGPPB4 exhibits the lowest transparency value
of 80.1% among the coatings, which is consistent with the obser-
vation of GPPB4 flame retardant. The above results show that a
moderate content of GO is essential to maintain the high trans-
parency of fire-retardant coatings.
The fractured surfaces of MGPPB3 are observed by optical digital
microscope (as seen in Fig. 1) and SEM (as seen in Fig. 5). It can be
seen from Fig. 1 that the natural appearance of wood surfaces is
clearly visible after application of MGPPB3 coating. As shown in
Fig. 5, the GO sheets are uniformly distributed and completely
exfoliated in the coating matrix. In general, the loss of transparency
for transparent polymer nanocomposites is ascribed to the scat-
tering of light by nanoparticles, and the well dispersion of GO with
dimensions less than the wavelength of visible light can effectively
minimize scattering phenomenon and achieve a high level of
transparency [22]. This is the reason why the incorporation of GO in
the transparent coatings retains a high level of transparency (as
seen in Fig. 4).
XRD is employed to analyze the structure of GO and the MGPPBs
(Fig. 6). The sharp diffraction peak of GO at 2q ¼ 11.2
features an
interlayer spacing of 0.79 nm, corresponding to the diffraction of
(002) plane of GO. In addition, a weak and broad peak of GO ap-
pears at 2q ¼ 21.1
corresponding to an interlayer spacing of
0.42 nm, which is caused by unexfoliated graphite [30]. After
introduction of GO into the coatings, the two major diffraction
peaks of GO disappear in the MGPPB3 and MGPPB4, indicating that
the amino resin and PPB are intercalated into the layers of GO that
achieve well dispersion and completely exfoliated state of GO
nanosheets. This is consistent with the observation from SEM
images.
3.3. Hardness and adhesion analyses
The pencil hardness and adhesion classification of the coatings
are listed in Table 2. It can be seen that the introduction of GO
slightly increases the pencil hardness of the coatings, and the pencil
hardness of MGPPB4 is increased to 2B. In addition, the adhesion
classification of the coatings is slightly increased to 2B and then the
decreased to 3B with increasing GO content, indicating that a
moderate content of GO is beneficial to impart the optimum
adhesion property to the coatings. And, an excessive content of GO
will greatly decrease the acid number of the organophosphate
concomitant with the decrease of cross-linking activity, resulting in
the decrease of crosslinking density and adhesion property of the
amino coatings.

Fig. 7. Digital photographs of the char residues after the cabinet method test.
 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064
Fig. 8. Backside time-temperature curves of the samples assessed by the big panel
method test.
3.4. Fire protection tests
The results from the cabinet method and tunnel method tests
are listed in Table 3. It can be found that the application of trans-
parent fire-retardant coatings greatly decreases the weight loss,
char index and FSR values of the samples, indicating the
improvement of fire protection performance. In addition, the
introduction of GO can further improve the fire protection perfor-
mance of the samples, and MGPPB3 exhibits the lowest weight loss
(2.3 g), char index (3.3 cm3) and FSR (6.9) concomitant with the
highest intumescent factor of 90.5 among the samples. By
combining Fig. 7, it can be found that the coatings containing GO
generate a more compact and intumescent char that provides an
effective physical barrier against the heat and mass transfer, and
MGPPB3 exhibits the densest and highest char among the samples
in accordance with the best fire protection performance. In addi-
tion, it is noted that an excessive content of GO will suppress the
swelling process and diminish its positive effect on improving the
barrier effect and fire protection performance of the coatings.
The heat insulation property of the coatings was assessed by the
big panel method test, and the results are presented in Fig. 8. It can
be seen that the backside temperature of uncoated sample in-
creases rapidly and reaches 247.3
C at 200 s, and the application of
the coatings gradually decreases the backside temperature of the
samples. From MGPPB0 to MGPPB4, the equilibrium backside
temperature at 900s is 229.3, 205.4, 189.4, 156.9 and 168.8
C,
respectively. In particular, MGPPB3 exhibits the best heat insulation
property as well as fire protection performance among the samples,
coinciding with that obtained by the cabinet method and tunnel
method tests. Based on the above results, it can be found that the
introduction of GO exerts excellent synergistic effect on enhancing
the fire protection performance of the transparent coatings, and
this synergistic effect depends on the content of GO.
3.5. Smoke density test
Light absorption curves of the transparent fire-retardant coat-
ings are presented in Fig. 9. It can be seen that the light absorption
value of the coatings continuously increases and reaches the
maximum value at 240 s. When GO is introduced, the GPPBs impart
lower light absorption values to their resulting coatings than those
7
Fig. 9. Light absorption curves of the transparent fire-retarded coatings.
of PPB, indicating the reduction of smoke release. In particular,
MGPPB3 containing GPPB3 exhibits the lowest light absorption
value of 31.8% at 240 s, and this value is 42.6% lower than that of
MGPPB0 containing PPB.
The smoke density rating (SDR) values of the coatings are pre-
sented in Fig. 10. It is obviously seen that the introduction of GO
greatly decreases the SDR value of the coatings, and MGPPB3
possesses the lowest SDR value of 14.2% concomitant with the best
smoke suppression effect among the samples. From the above re-
sults, it can be concluded that the introduction of GO performs well
synergistic smoke suppression effect in the transparent coatings,
and an excessive content of GO will diminish the smoke suppres-
sion efficiency.
3.6. Cone calorimeter test
The heat release rate (HRR) and total heat release (THR) curves
of the transparent fire-retardant coatings are presented in Fig. 11a
and Fig. 11b, respectively. It can be observed that MGPPB0 burns
rapidly after ignition with the highest peak HRR (PHRR) value and
THR value of 120.4 kW/m2 and 2.4 MJ/m2, respectively. As expected,
the introduction of GO decreases the PHRR and THR values of the
coatings, indicating that the presence of GO is effective in reducing
the heat release of the coatings. In detail, the PHRR values from
MGPPB1 to MGPPB4 are 113.6, 106.8, 90.8 and 96.6 kW/m2,
respectively, and the THR values from MGPPB1 to MGPPB4 are 2.1,
2.0, 1.6 and 1.8 MJ/m2, respectively. Among the above coatings,
Fig. 10. Smoke density rating (SDR) values of the transparent fire-retarded coatings.
8 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064

MGPPB3 exhibits the lowest PHRR and THR values, and these values
are reduced by 24.6% and 33.3%, respectively, compared to the
values of MGPPB0. By combining the char residues of Fig. 11c, it can
be found that the introduction of GO is beneficial to produce a more
compact and intumescent char that effectively prevents the un-
derlying materials from further combustion, thus exhibiting less
heat release during burning. In particular, MGPPB3 shows the
highest intumescent char concomitant with the lowest heat release
among the samples, further verifying that a moderate content of GO
is crucial to exhibit the optimum synergistic flame-retarded effect
in the coatings. This is consistent with the results obtained from the
fire protection tests.

3.7. TG analysis

The TG and DTG curves of the transparent fire-retardant coat-

ings are presented in Fig. 12, and the related data are listed in
Table 4. And, Ton is defined as the onset decomposition temperature
at 5% weight loss, Tmax means the temperature of peak mass loss
rate, and PMLR is defined as the mass loss rate at Tmax.
It can be observed from Fig. 12 that the coatings exhibit five
decomposition processes in the temperature ranges of 60e200
C,
200e280
C, 280e450
C, 450e550
C and 550e700
C. The first
stage at 60e200
C is ascribed to the release of small molecules
accompanying with a little weight loss (<7.5 wt%). The second stage
at 200e280
C corresponding to a strong DTG peaks is ascribed to
the breakage of PeOeC groups in the structure of PPB and the
GPPBs, and the GPPBs impart higher PMLR value and weight loss to
the resulting coatings than those of PPB at this stage. The third
stage at 280e450
C is the dominated one and is assigned to the
decomposition of flame retardants and amino resin. In this stage,
the phosphate derivatives and ethylene glycol ester released from
phosphate interact with triazine compounds and incombustible
gases released from amino resin to form multicellular char layer.
The fourth stage at 450e550
C is ascribed to the aromatization and
polymerization of unstable double bonds or structures, corre-
sponding to a weak DTG peak. The fifth stage at 550e700
C is
Fig. 12. TG (a) and DTG (b) curves of the transparent fire-retardant coating under
assigned to the decomposition of unstable carbonized backbones in
nitrogen atmosphere at a heating rate of 10
C/min.
the char residues.

Fig. 11. Heat release rate curves (a), total heat release curves (b) and digital photos of char residues (c) of the transparent fire-retardant coatings after the cone calorimeter test.
 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064 9

Table 4 Table 5
Thermal parameters of the transparent fire-retardant coatings under nitrogen at- XPS data of the char residues obtained after the cabinet method test.
mosphere at a heating rate of 10
C/min.
Samples C, at% O, at% N, at% P, at% B, at% O/C N/C P/C
Samples Ton/
C Tmax/
C PMLR/(%/min) Residue at 700
C/%
MGPPB0 50.5 34.0 6.1 7.1 2.3 0.67 0.12 0.14
MGPPB0 171.2 270.2b, 329.2c,486.3d 2.1b,3.0c,1.6d 31.1 MGPPB3 31.2 47.3 7.7 10.3 3.5 1.52 0.25 0.33
MGPPB1 176.4 253.6b,330.8c,492.7d 3.4b,2.6c,1.6d 31.9
MGPPB2 179.5 253.6b,333.9c,495.9d 3.2b,2.5c,1.5d 32.9
MGPPB3 183.3 255.3b,332.7c,492.4d 3.0b,2.2c,1.4d 34.5
MGPPB4 186.1 253.6b,332.3c,486.3d 2.9b,2.4c,1.4d 33.7 crosslinking structures in the condensed phase that can enhance
Note: superscript b represents the second degradation stage, c denotes the third
the barrier effect and thermal stability of char. In addition, the high
degradation stage, and d illustrates the fourth degradation stage. C/O ratio in the char residue of MGPPB3 further illustrates that the
introduction of GO contributes to enhance the cross-linking density
and anti-oxidation ability of the char residue, thus exhibiting better
As shown in Table 4, it can be seen that the introduction of GO compactness and barrier effect.
greatly improves the Ton and residual weight at 700
C of the
coatings concomitant with the decrease of mass loss rate and PMLR
3.9. XPS analysis
at the main decomposition stage, indicating the enhancement of
thermal stability and char formation. And, the increased residual
The elemental information and chemical structures of the char
weight is beneficial for reducing the amounts of combustible gases
residues after the cabinet method test are analyzed by XPS, and the
and smoke precursors during combustion, thus decreasing the heat
detailed composition is listed in Table 5. As shown in Table 5, the O/
release and smoke production. In particular, MGPPB3 exhibits
C, N/C and P/C ratios of MGPPB3 char are higher than those of
highest residual weight of 34.5% at 700
C among the samples,
MGPPB0, indicating more P, N and O-containing cross-linking
corresponding to the lowest smoke production and heat release.
structures remained in the MGPPB3 char. This result can be
According to above results, it can be concluded that the introduc-
ascribed the fact that the barrier effect of GO sheets can effectively
tion of GO plays a positive effect on improving the thermal stability
reduce the release of NH3, volatile phosphorus and boron, thus
and char formation of the coatings.
leaving more P, N and B for char formation.
The full-scan XPS spectra and high-resolutions of C1s, N1s, O1s,
3.8. SEM-EDS analysis P2p and B1s XPS spectra of the char residues after the cabinet
method test are presented in Fig. 14, and the corresponding results
The SEM images and EDS maps of the char residues after the are listed in Table 6. As shown in Fig. 14a, the char residues of
cabinet method test are shown in Fig. 13. As can be observed from MGPPB0 and MGPPB3 mainly contain carbon, nitrogen, oxygen,
Fig. 13a that the char residue of MGPPB0 has a lot of voids and holes phosphorus and boron elements. The C1s spectra present three
with different sizes that provide channels for the transport of ox- bands at 284.5, 285.0 and 286.3 eV as shown in Fig. 14b, and the
ygen and combustible volatiles between the inner matrix and the peak at 284.5 eV is assigned to the CeH and CeC groups of aliphatic
flame. In Fig. 13b, the char residue of MGPPB3 is very compact and and aromatic species [31]. As for N1s spectra, three bands are found
continuous with few holes and voids, thus providing an effective at 399.5, 400.2 and 402.1 eV that can be assigned to the C]N
physical barrier against the heat transfer and mass transportation. groups in triazine rings, CeN groups and NeH groups, respectively
The results of EDS maps show that MGPPB3 remains more P and B [32,33]. As shown in Fig. 14d, the O1s spectra show two bands at
elements in the char residue than that of MGPPB0. Generally, the 531.6 and 533.1 eV that is assigned to the ¼ Oe groups (C]O and
char residue rich in P and B elements is beneficial to generate more P]O groups) and eOe groups (CeOeC, PeOeP and/or CeOH

Fig. 13. SEM images and EDS maps of the char residues after the cabinet method test: (a) MGPPB0 and (b) MGPPB3.
10 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064

Fig. 14. XPS spectra of the char residues obtained from the cabinet method test: (a) a full-scan, (b) C1s XPS spectra, (c) N1s XPS spectra, (d) O1s XPS spectra, (e) P2p XPS spectra, and
(f) B1s XPS spectra.

groups), respectively [34]. The P2p spectra present two bands at
134.0 and 134.6 eV as shown in Fig. 14e that can be assigned to the
PeOeC, PeOeP and/or PO 3 groups in phosphorus-rich cross-links
[35]. As shown in Fig. 14f, two peaks at 190.2 and 192.2 eV in the B1s
spectra can be attributed to BeO groups (BeOH and BeOeB) and
BeOeC groups, respectively [16].
It can be observed from Table 6 that MGPPB3 produces more
CeN, PeOeC, PeOeP and BeOeC groups in the char compared to
those of MGPPB0, revealing that the introduction of GO is beneficial
for generating more crosslinking structures that enhance thermal
 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064 11

Table 6
Fitting results of C1s, N1s, O1s, P2p and B1s spectra of the char residues obtained after the cabinet method test.

Elements Binding energy/eV Groups MGPPB0/at% MGPPB3/at%

C1s 284.5 CeH and CeC 8.7 6.9

285.0 CeO, CeN and CeOeP 26.0 13.9
286.3 C¼O, C]C and C]N 15.8 10.4

N1s 399.5 C¼N 0.7 1.1

400.2 CeN 2.8 3.4
402.1 NeH 2.6 3.2

O1s 531.6 ¼ Oe group 12.4 23.0

533.1 eOe group 21.6 24.3

P2p 134.0 PeO and/or PO3 1.7 4.8

134.6 PeOeC 5.4 5.5

B1s 190.2 BeO 0.3 0.8

192.2 BeOeC 2.0 2.7

stability and barrier effect of char against the mass transportation
and heat transfer during burning.
3.10. Flame-retardant and smoke suppression mechanism
An illustration of the potential flame-retardant and smoke
suppression mechanism of the GPPBs in the transparent fire-
retardant coatings is presented in Fig. 15. The mechanism of the
GPPBs in the transparent coatings is ascribed to both gas phase and
condensed phase mechanisms. When exposed to heat or flame, the
coatings begin to decompose and release incombustible gases (H2O
and NH3) that dilute the combustibles gases and reduce the com-
bustion intensity. With the temperature increasing, the
phosphorus-based species (mainly PO$ and P$ radicals) released
from PPB and GPPBs react with free radicals (mainly HO$ and H$
radicals) produced by amino resin, which can effectively reduce the
degradation products of the coatings escaping into the gas phase.
As a result, the decrease of degradation products leads to a
reduction in smoke production and heat release during burning.
More importantly, the interaction between GO sheets and phos-
phate ester or its derivatives leads to generate more crosslinking
structures in the condensed phase that strengthen the compact-
ness, anti-oxidation ability and insulation property of the char
layer, whose “barrier effect” could effectively isolate the heat, ox-
ygen and combustible gas transfer, thus preventing the underlying
materials from further combustion. Based on the above discussion,
the flame retardancy and smoke suppression properties of the
coatings containing GPPBs are greatly improved.
4. Conclusions
In this work, a series of efficient organophosphate-
functionalized GO flame retardants (GPPBs) were synthesized by
functional modification of graphite oxide with PPB, and FTIR and 1H
NMR spectra confirm the successful grafting of PPB on the surface
of GO. Then, the obtained GPPBs were incorporated into amino

Fig. 15. Potential flame-retardant and smoke suppression mechanism of the GPPBs in the transparent fire-retardant coatings.
12 L. Yan et al. / Polymer Degradation and Stability 172 (2020) 109064
resin to produce transparent fire-retardant coatings. The results
show that the introduction of GO can improve the hardness and
adhesion property of the coatings, and MGPPB3 shows the best
adhesion property among the samples. Transparency analysis re-
veals that the uniform dispersion and completed exfoliated states
of GO sheets in the amino matrix can retain the high transparency
in the coatings even at high GO contents, as determined by XRD
pattern and SEM images. Fire protection tests show that the uni-
form dispersion of GO sheets can greatly decrease the weight loss,
char index and FSR values of the coatings concomitant with the
increase of insulation property and intumescent factor, and
MGPPB3 possesses the lowest SDR value of 14.2% and highest
intumescent factor of 90.5 among the samples. Cone calorimeter
and smoke density tests indicate that the presence of GO sheets
greatly decreases the heat release and smoke production of the
coatings, exhibiting excellent synergistic flame retardant and
smoke suppression effects. Especially, MGPPB3 shows the best
synergistic effect among the samples, for example, 60.7% reduction
in SDR value and 33.3% reduction in THR value are observed for
MGPPB3 compared to those of MGPPB0. TG results show that the
introduction of GO plays an positive effect on improving the ther-
mal stability and char formation of the coatings, and MGPPB3 ex-
hibits the highest residual weight of 34.5% at 700
C. Char residue
analysis shows that the remarkable enhancements in the flame
retardancy and smoke suppression properties are largely ascribed
to the high-quality char with outstanding compactness, anti-
oxidation ability and insulating property, which are able to isolate
the transport of volatile degradation products and heat between
gas phase and condensed phase during burning. And, the
improvement in the yield, anti-oxidative ability and barrier effect of
intumescent char is mainly attributed to the fact that the intro-
duction of GO results in the formation of more crosslinking struc-
tures containing CeN, PeOeC, PeOeP and BeOeC groups in the
condensed phase. In summary, the results provide a new insight
into the application of functionalized GO in the design and prepa-
ration of super transparent fire-retardant coatings.
Authors’ contributions
Long Yan: Conceptualization, Methodology, Supervision,
Writing-Review and Editing. Zhisheng Xu: Supervision, Validation,
Project Administration, Writing-Review and Editing. Nan Deng:
Data Curation, Investigation, Visualization.
Declaration of competing interests
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Nos. 51676210 and 51906261) and the Natural
Science Foundation of Hunan Province (No. 2018JJ3668).
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