Chemical Engineering Journal 369 (2019) 8–17

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Chemical Engineering Journal

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

A highly efficient flame retardant nacre-inspired nanocoating with T

ultrasensitive fire-warning and self-healing capabilities
⁎ ⁎
Huali Xiea, Xuejun Laia, , Hongqiang Lia, Jiefeng Gaob, Xingrong Zenga, , Xiaoyi Huanga,
Xiaoyong Lina
a
College of Materials Science and Engineering, Key Lab of Guangdong Province for High Property and Functional Polymer Materials, South China University of Technology,
Guangzhou 510641, China
b
College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Afabricated
nacre-inspired nanocoating was
via one-step self-assembly.
• The nanocoating triggered the fire-
warning in less than three seconds
when encountering fire.
• The nanocoating endowed many
combustible substrates with super-ef-
ficient flame retardancy.
• The damaged nanocoating could self-
heal quickly in room temperature.

A R T I C LE I N FO A B S T R A C T

Keywords: Design and exploitation of flame retardant coatings with sensitive fire-warning response and self-healing cap-
Self-healing ability are urgently needed to decrease the fire risk of combustible materials. Herein, we reported the fabrication
Fire-warning of a novel multifunctional flame retardant nanocoating created by using graphene oxide (GO) and functional
Flame retardant nanocoating cellulose (FC) via one step self-assembly. The prepared nacre-like nanocoating endowed many kinds of com-
Graphene oxide
bustible materials (including polypropylene, polyurethane foam and wood) with exceptional fire safety. All the
Cellulose
coated substrates were self-extinguished in the flame retardant tests. More importantly, when being attacked by
fire at the very early stage, it triggered the fire-warning in less than three seconds through the dramatic decrease
of electrical resistance. Moreover, the nanocoating exhibited outstanding self-healing capability at room tem-
perature. Due to the multiple hydrogen bondings between the ureido pyrimidinone groups on FC, the damaged
coating could be healed successfully and almost recovered to its original integrated performance. Our work
provides a new and effective route to remarkably improve the fire safety of the combustible materials, exhibiting
an enticing prospect for its application in the fields of building, transportation and electrical equipment.

1. Introduction especially in the fields of building, decoration, transportation, furniture,

cable and electrical equipment [1,2]. However, many common light
The society is showing an increasing demand for light materials, materials, such as polymers and woods, are highly combustible and

⁎
Corresponding authors at: College of Materials Science and Engineering, Key Lab of Guangdong Province for High Property and Functional Polymer Materials,
South China University of Technology, No 381, Wushan Road, Tianhe District, Guangzhou 510640, China.
E-mail addresses: msxjlai@scut.edu.cn (X. Lai), psxrzeng@gmail.com (X. Zeng).

https://doi.org/10.1016/j.cej.2019.03.045
Received 13 December 2018; Received in revised form 28 February 2019; Accepted 7 March 2019
Available online 07 March 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
H. Xie, et al.
their wide applications are exacerbating fire safety problems [3,4]. In
recent years, the frequency of large fire accidents caused by the use of
polymers and woods is increasing [5]. On June 14, 2017, the London
Granfield tower fire accident which was caused by the ignition of
combustible thermal insulation materials of the exterior wall, led to 79
deaths. More worryingly, there are countless similar high-rise re-
sidential buildings all over the world, which have greatly raised peo-
ple’s concern about their fire safety. Not only the flammability of the
building materials, but also the fire-warning system of the buildings are
the key factors that influence the fire spreading and hence the escaping
time for the residents at the early stage.
Although there is a large number of commercial fire-warning sys-
tems including smoke detectors and infrared flame detectors in the
market, their early-warning and fire prevention effect is unsatisfactory.
On August 13, 2018, a serious fire accident caused by the short circuit
of an automatic bed took place at a hospital in New Taipei city, Taiwan.
Because of the high combustibility of the foam mattress and the delay of
the fire-warning, the fire was out of control and caused 9 deaths.
Although the fire detectors and sprinkler system worked normally, it
was too late to curb the fire spread. The cause of this tragedy was that
the existing fire detectors were located at a certain distance from the
combustion source; moreover, only when the smoke concentration or
the infrared detection temperature reached a critical value could the
fire detectors be triggered [6]. Accordingly, the fire-warning response
was insensitive (the response time was more than 100 s) [7], missing
the best chance for people’s evacuation and also making it much more
difficult to put out the fire. Given the above, it is therefore of great
emergency and importance to shorten the fire-warning time. Endowing
combustible materials with self-warning property will be one of the
most effective methods to achieve the point.
Recently, multifunctional coatings have attracted more and more
attentions. By introducing functional molecules or groups, the coatings
can respond intelligently to the change of the surrounding environment,
including strain [8], temperature [9], pH [10,11], moisture [12] and
light [13,14]. Applying the temperature-responsive coating on com-
bustible materials is considered to be an effective method to realize
their sensitive self-warning, because the coating will contact the fire
before the combustible materials and warn of the danger rapidly. Wu
and co-workers [15] developed a fire-warning coating based on gra-
phene oxide (GO) and silicone. The coating showed distinct tempera-
ture-responsive electrical resistance change because GO could be
quickly reduced to graphene at a high temperature, and it exhibited a
rapid flame detection response in about 3 s when encountering fire.
Moreover, the coating significantly improved the flame retardancy of
the polymer substrates. Nevertheless, comparing with the traditional
fire detectors, polymer coatings are prone to fatigue and damnification
especially under mechanical deformation [16,17], which severely da-
mages the reliability of self-warning flame retardant coatings and
brings a big challenge to their practical application. Thus, it is desirable
that the self-warning flame retardant coatings can self-heal when they
are partially or even completely damaged during the practical appli-
cation.
Inspired by the self-healing capability of skin, self-healing materials
have attracted increasing attention, especially in the fields of polymer-
based sensor [18–20], nanogenerator [21] and artificial muscle [22]. In
general, the self-healing capability of polymers is due to the abundant
reversible covalent bonding [23,24] or noncovalent bonding [25,26]
formed by the introduced functional groups. Among them, ureido
pyrimidinone (UPy) groups, which can form self-complementary
quadruple hydrogen bondings with each other [27], have attracted
considerable attention and have been applied to prepare self-healing
coatings [28], films [29] and hydrogels [30]. For example, Yan and co-
workers [29] utilized UPy groups to endow their thin film electrodes
with desirable self-healing capability. Besides, UPy groups can form
hydrogen bondings with the oxygen-containing groups on GO na-
nosheets [31]. Therefore, introducing UPy groups into the polymer
9
Chemical Engineering Journal 369 (2019) 8–17
coating based on GO is proposed to be an effective approach to en-
dowing it with good self-healing capability.
Herein, a functional cellulose (FC) was firstly synthesized by
grafting UPy groups on hydroxypropyl methyl cellulose (HMC).
Subsequently, it was combined with GO to fabricate a multifunctional
flame-retardant nanocoating on combustible materials (including
polypropylene, polyurethane foam and wood) by one-step self-as-
sembly. The GO/FC nanocoating exhibited ultrasensitive fire-warning
property and exceptional fire safety, as well as outstanding self-healing
capability. Our work provides a new and effective route to remarkably
improve the fire safety of the combustible materials, exhibiting an en-
ticing prospect for its application in the fields of building, transporta-
tion and electrical equipment.
2. Experimental section
2.1. Materials
Graphite powder (99.9%), 2-amino-4-hydroxy-6-methylpyrimidine
(AHM, 98.0%), 1,6-diisocyanatohexane (99.0%) and hydroxypropyl
methyl cellulose (HMC, 100 mPa·s) were purchased from Aladdin
Reagent Co., Ltd., China. Sodium nitrate (NaNO3) and potassium per-
manganate (KMnO4) were purchased from Sigma-Aldrich Co., Ltd.,
China. Sulfuric acid (H2SO4, 96 wt%) and hydrochloric acid (HCl, 37 wt
%) was produced by Zhuhai Huachengda Chemical Co., Ltd., China.
Hydrogen peroxide (H2O2, 30 wt%) was produced by Sinopharm
Chemical Reagent Co., Ltd., China. Dibutyltin dilaurate (DBTDL) was
purchased from Shanghai Macklin Biochemical Co., Ltd., China.
Dimethyl sulfoxide (DMSO), n-pentane and isopropanol were produced
by Guangzhou Chemical Reagent Factory, China. All the reagents were
used as received without further purification.
Three kinds of combustible materials were applied as the coating
substrates. Polypropylene bar was prepared by us [32]. Polyurethane
(PU) foam with a density of 22.4 kg/m3 was produced by Guangzhou
Weida Sponge Products Factory, China. Pinus sylvestris bar was pur-
chased from Guangzhou Dante Environmental Science and Technology
Co., Ltd., China.
2.2. Synthesis of GO
GO was synthesized according to a modified hummers method
[33].Briefly, 3.00 g NaNO3 and 6.00 g graphite powder was dispersed in
140 mL concentrated H2SO4 with the assistance of stirring at 0–3 °C.
After 30 min of stirring, 20.00 g KMnO4 was added into the dispersion
slowly within 2 h, followed by 1 h of reaction at 0–3 °C and 1.5 h of
reaction at 38 °C. Then 300 mL deionized water was added into the
dispersion and the reaction proceeded at 85 °C for 15 min. The reaction
was terminated by adding 500 mL deionized water, 16 mL H2O2 (30 wt
%) and 12 mL HCl (37 wt%) in sequence. The dispersion was cen-
trifuged and the obtained precipitation was washed with deionized
water until the pH of the supernatant reached 7. After dried in a va-
cuum oven at 50 °C for 12 h, GO was obtained and its morphology was
studied with atomic force microscopy (AFM, Fig. S1a) and transmission
electron microscopy (TEM, Fig. S1b).
2.3. Synthesis of functionalized cellulose (FC)
(1) Synthesis of 2(6-isocyanatohexylaminocarbonylamino)-6-methyl-
4[1H] pyrimidinone (UPy-NCO). UPy-NCO was synthesized ac-
cording to a reported method [34]. Briefly, 4.00 g AHM was dis-
persed in 36.00 g HDI with the assistance of stirring. Under the
protection of nitrogen, the reaction was carried out at 100 °C for
20 h. After cooled to ambient temperature, 50 mL n-pentane was
added into the solution to precipitate the reaction product. The
obtained precipitation was filtered and washed with n-pentane for
several times. After dried in a vacuum oven at 50 °C for 12 h, UPy-
H. Xie, et al.
Fig. 1. (a) Synthesis route of FC. (b) Preparation route of GO/FC nanocoating on polymer substrate.
NCO was obtained.
(2) Synthesis of FC. As shown in Fig. 1a, 1.00 g UPy-NCO, 4.00 g HMC
and 0.06 g DBTDL were dissolved in 100 mL DMSO with the assis-
tance of stirring. Under the protection of nitrogen, the reaction was
carried out at 100 °C for 12 h. After cooled to ambient temperature,
200 mL isopropanol was added into the solution to precipitate the
reaction product. The obtained precipitation was filtered and wa-
shed with isopropanol for several times. After dried in a vacuum
oven at 50 °C for 12 h, FC was obtained. Through Fourier transform
infrared spectroscopy (FTIR, Fig. S2a), it was proved that FC was
successfully synthesized.
2.4. Preparation of GO/FC nanocoatings on substrates
As shown in Fig. 1b, GO and FC with different mass ratios were
dispersed in deionized water with the assistance of stirring and ultra-
sonic. The total concentration of the dispersions was 1.0 wt%. The
obtained dispersions were named GO/FC-n (n represented the GO
content in GO/FC system and the values of n were 20 wt%, 30 wt%,
40 wt%, 50 wt% or 60 wt%). The nanocoatings were fabricated on
substrates through dip-coating. Before the coating process, PP bars and
wood bars were plasma-treated in a vacuum plasma surface treatment
equipment (PlasmaFlecto 10, Plasma Technology Inc., Germany) in
oxygen atmosphere under 0.2 mbar for 6 min. Then treated PP bars and
wood bars were dipped in the dispersions for 20 s and hung vertically in
the oven at 60 °C for about 15 min. After the bars were dry, they were
turned by 180°, dipped in the dispersions and dried in the oven again.
The dip-coating process on the bars was repeated for 10 times. PU
foams were dipped in the dispersions for 10 min and the excessive
dispersion was shaken off. Then they were dried in oven at 80 °C for
24 h. The obtained coated PP, wood and PU were named PP-GO/FC-n,
Wood-GO/FC-n and PU-GO/FC-n (n represented the GO content in GO/
FC system and the values of n were 20 wt%, 30 wt%, 40 wt%, 50 wt% or
60 wt%), respectively. For comparison, GO and FC dispersions with a
concentration of 1.0 wt% were prepared and applied to coated PP bars
in the same method, and the obtained coated PP were named PP-GO
and PP-FC, respectively.
2.5. Characterization
The morphology of the as-prepared GO nanosheet was studied with
a Multimode 8 atomic force microscope (Bruker Optics Inc., Germany)
and a JEM-2100F transmission electron microscope (JEOL, Japan). The
morphology and chemical compositions of the as-prepared coatings
10
Chemical Engineering Journal 369 (2019) 8–17
were studied on a Merlin field emission scanning electron microscopy
(Carl Zeiss Jena, Germany) equipped with an X-MaxN20 energy dis-
persive X-ray spectrometry (Oxford Instruments, Britain). The Fourier
transform infrared spectroscopy (FTIR) was conducted on a TENSOR27
infrared spectrometer (Bruker Optics Inc., Germany). The X-ray dif-
fraction (XRD) was performed on an X’Pert Pro X-ray diffractometer
(PANalytical, Netherlands). The flame retardancy tests were conducted
on a JF-3 oxygen index meter (Nanjing Jiangning Analytical Instrument
Co., Ltd., China) and a CZF-3 horizontal vertical burning meter
(Nanjing Jiangning Analytical Instrument Co., Ltd., China). The elec-
trical resistance changes of the nanocoatings during fire-warning test
were recorded with an ESCORT 3146A multimeter. The oxygen per-
meability was investigated on a VAC-V2 gas permeameter (Labthink
Instruments Co., Ltd., China). The thermogravimetry-Fourier transform
infrared spectrometry (TG-FTIR) was conducted on a TENSOR27 in-
frared spectrometer (Bruker Optics Inc., Germany) coupled with a
TG209 thermogravimeter (Netzsch Instruments Co., Ltd., Germany).
The X-ray photoelectron spectroscopy (XPS) was carried out on an Axis
Ultra DLD X-ray photoelectron spectrometer (Kratos Co., Ltd., Britain).
3. Results and discussion
3.1. Characterization of GO/FC nanocoatings
As shown in Fig. 1, GO/FC nanocoatings were fabricated on sub-
strates through the one-step co-assembly of GO nanosheets and FC
molecular chains. Fig. S2d shows that after drying, the infrared char-
acteristic peak of the hydroxyl groups of GO shifted to lower wave-
number, indicating that the abundant UPy groups on FC molecular
chains formed multiple hydrogen bondings with the oxygen-containing
groups on GO nanosheets during drying. The co-assembly and hydrogen
bonding between GO nanosheets and FC molecular chains led to the
formation of nacre-like “brick and mortar” structure (Fig. 2g and h)
[35], which was proved by the cross section SEM images of the nano-
coatings shown in Figs. S3 and 2a–e. It was observed that the nano-
coatings exhibited nacre-like well-arranged hierarchical structure and
the thickness of the nanocoating grew uniformly with the increase of
the repeat number of dip-coating. When the repeat number of dip-
coating was increased to 10, the thickness of GO/FC-40 was about
102.2 μm. Besides, it was found that with the increase of the GO content
in the nanocoatings, the arrangement of the GO nanosheets became
tighter and more regular, which was consistent with the XRD results in
Fig. 2i. There was a single peak appearing at all the XRD spectra of the
nanocoatings, which was attributed to the (0 0 1) crystal plane
H. Xie, et al. Chemical Engineering Journal 369 (2019) 8–17

Fig. 2. Cross section SEM images of the nanocoatings: (a) GO/FC-20, (b) GO/FC-30, (c) GO/FC-40, (d) GO/FC-50, (e) GO/FC-60 and (f) GO. (g) Digital photo and (h)
cross section SEM image of nacre. (i) XRD spectra of the nanocoatings. The results indicated that the nanocoatings exhibited nacre-like well-arranged hierarchical
structure and the arrangement became tighter and more regular with the increase of the GO content in the nanocoatings.

diffraction of the GO nanosheets. With the increase of the GO content, Table 1

the (0 0 1) diffraction peak became sharper and stronger, and it gra- The fire-warning trigger time of the nanocoatings on the different substrates.
dually shifted towards higher 2θ values, indicating that the GO na- Nanocoatings Trigger time on different substrates (s)
nosheets tended to better arrangement and the layer spacing between
them was gradually shrunk. This was because with the increase of the PP Wood PU
GO content, the amount of the FC between GO nanosheets was de-
GO 4.0 4.3 3.3
creased, facilitating the orientation of GO nanosheets and thus the in- GO/FC-20 10.6 11.2 8.3
terlaminar stacking. However, the decrease of FC content in GO/FC GO/FC-30 7.1 6.5 6.4
system would sacrifice the stability of the formed nanocoating. The GO/FC-40 3.2 2.9 2.4
nacre-like well-arranged hierarchical structure of GO/FC nanocoatings GO/FC-50 2.7 2.7 2.3
GO/FC-60 3.7 3.5 3.0
was one of the most important reasons for their exceptional flame re-
tardant and fire-warning performance in the following tests.
electrical resistance curves of coated PP in the fire-warning test. It was
3.2. Fire-warning response found that when the coated PP encountered fire, their electrical re-
sistances were decreased by 4–6 orders of magnitude within several
The nanocoatings showed ultrasensitive fire-warning response and seconds. For example, the electrical resistance of PP-GO/FC-50 was
their fire-warning trigger time on different substrates are listed in decreased from 58.6 MΩ/cm to 1000 Ω/cm within 3 s, which was
Table 1. With the increase of the GO content in GO/FC nanocoatings, consistent with the fire-warning trigger time of PP-GO/FC-50. The
the fire-warning trigger time of the nanocoatings showed similar electrical resistance of PP-GO/FC-50 eventually stabilized at about
changing trend on different substrates. It was decreased first and then 350 Ω. Even after the fire source was removed, the electrical resistance
increased. For coated PP and wood, when the GO content was increased of PP-GO/FC-50 was only increased to about 450 Ω. The dramatic de-
to more than 30 wt%, the fire-warning trigger time was decreased to crease of the electrical resistance of coated PP was due to the reduction
less than 10 s. Most notably, as shown in Fig. 3a, when the GO content reaction of GO in high temperature environment [15,36]. Fig. 3c shows
was increased to 50 wt%, the nanocoating on PP triggered the fire- the XPS spectrum of PP-GO/FC-40 before and after burning. It was
warning lamp in only 2.7 s after encountered fire. Fig. 3b shows the

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H. Xie, et al. Chemical Engineering Journal 369 (2019) 8–17

Fig. 3. (a) Fire-warning test process of PP-GO/FC-50. (b) Electrical resistance curves of coated PP when they encountered fire. (c) XPS spectra of PP-GO/FC-40 before
and after burning. C 1s XPS spectrum of PP-GO/FC-40 (d) before and (e) after burning. Cross section SEM images of the char layers of (f) PP-GO/FC-40 and (g) PP-GO
after burning. (h) Fire-warning response mechanism of GO/FC nanocoating. The results indicated that GO was rapidly reduced to graphene with high electrical
conductivity and the carbonization products of FC bonded the graphene nanosheets together, forming stable multiple conductive paths and triggering the fire-
warning lamp.

found that the after burning, the oxygen content of PP-GO/FC-40 was
decreased from 37.3% to 9.5%. Fig. 3d shows that the carbon-con-
taining components of PP-GO/FC-40 included 20.4% CeO (286.6 eV)
and 18.1% C]O (287.8 eV), which were attributed to the hydroxyl
groups on FC chains and the hydroxyl groups, epoxy groups, carboxyl
groups on GO nanosheets. After burning, as shown in Fig. 3e, the CeO
and C]O contents of PP-GO/FC-40 were decreased to 11.0% and 6.5%,
indicating that most of the oxygen-containing groups had been de-
composed and GO had been reduced to graphene which possessed a
much higher electrical conductivity.
However, when the GO content further increased to 60 wt%, the
fire-warning trigger time was increased instead of decreased. Even so,
the fire-warning trigger time of GO/FC-60 nanocoating was still shorter
than that of GO nanocoating. Moreover, it was found from Fig. 3b that
after burning, the electrical resistance of all the GO/FC nanocoatings
was much lower than that of GO nanocoating. The results indicated that
FC also played an important role in the fire-warning response of GO/FC
nanocoating. Fig. 3f and g shows the cross section SEM images of the
formed char layers of PP-GO/FC-40 and PP-GO after burning. In the
char layer of PP-GO/FC-40, the reduced GO nanosheets were in series
with each other, forming multiple conductive paths. By contrast, the
char layer of PP-GO was loose and there were many cracks on the
formed conductive paths, which indicated that the carbonization
products of FC played important bonding effect during the formation of
the char layer, effectively enhancing the continuity of the conductive
paths. Based on the above results, as shown in Fig. 3h, the fire-warning
mechanism of GO/FC nanocoating was proposed. When encountering
fire, GO was rapidly thermally reduced to graphene with a high elec-
trical conductivity through the decomposition of the oxygen-containing
groups. Meanwhile, the carbonization products of FC bonded the gra-
phene nanosheets together, forming stable multiple conductive paths
and triggering the fire-warning lamp.
Moreover, even for PU foam with porous structure, GO/FC nano-
coating possessing a uniformly hierarchical structure could also be
fabricated on it and endowed it with ultrasensitive fire-warning re-
sponse. As shown in Fig. 4a1 and Fig. 4b1, with a thickness of only
about 1 μm, the fabricated hierarchical GO/FC nanocoating coated the
skeleton of the PU foam tightly and had little influence to the porous
morphology of PU foam. The coated PU foam still exhibited excellent
elasticity and deformation restorability (Fig. S4). Moreover, due to the
large contact area, the coated PU foam responded to the fire more ra-
pidly than the coated PP and wood. Table 1 and Fig. S5b show that PU-
GO/FC-40 triggered the fire-warning lamp in only 2.4 s after en-
countered fire. It was found from Fig. 4a2 and b2 that, after burning,
the PU foam skeleton remained intact while the GO/FC nanocoating
was transformed into hierarchical conductive paths. The interconnected

12
H. Xie, et al.
Fig. 4. (a, b) SEM images and (c) EDX spectra of the cross sections of PU-GO/FC-40 (1) before and (2) after fire-warning test. The insets in (a1) and (a2) were the
corresponding digital images of PU-GO/FC-40 before and after fire-warning test.
structure of PU foam skeleton facilitated the construction of the con-
ductive network.
3.3. Flame retardancy
In order to further evaluate the fire protection effect of GO/FC na-
nocoating, limiting oxygen index, vertical burning and horizontal
burning tests were utilized to study the flame retardancy of the coated
PP, wood and PU foam, and the results were shown in Table 2, Figs. 5,
S6 and S7. With the LOI value of 18.0%, 26.5% and 17.5%, respec-
tively, PP, wood and PU foam were highly combustible in the flame
retardancy tests. They were easy to ignite and the flame spread rapidly
on them, followed by violent burning. They reached no rating in the
vertical burning test and only reached the ratings of FH-3-26 mm/min,
FH-4-51 mm/min and FH-4-188 mm/min in the horizontal burning test,
respectively. The burning of PP and PU foam were even accompanied
with severe melt dripping until they were totally burnt out. The instant
ignition of these materials and the rapid spread of the flame always
made the current fire prevention system fail to give an early warning.
13
Chemical Engineering Journal 369 (2019) 8–17
After decorated by GO/FC nanocoatings, the fire-safety of these com-
bustible materials was remarkably improved. Especially when the GO
content in GO/FC nanocoating was 40 wt%, GO/FC nanocoating ex-
hibited most significant fire protection effect. The LOI values of PP-GO/
FC-40, Wood-GO/FC-40 and PU-GO/FC-40 were as high as 31.0%,
41.5% and 25.5%, respectively. Meanwhile, PP-GO/FC-40, Wood-GO/
FC-40 and PU-GO/FC-40 all self-extinguished in vertical and horizontal
burning tests. They all reached V-0 rating in the vertical burning test
and reached FH-1, FH-1 and FH-2 ratings in the horizontal burning test,
respectively. As shown in Figs. 5 and S6, PP-GO/FC-40 and Wood-GO/
FC-40 were hard to ignite, because a protective char layer was formed
on the surface of them immediately when they contact with the fire.
After the fire source was removed, the residual flame on PP-GO/FC-40
and Wood-GO/FC-40 was self-extinguished in about 0.5 s and 2 s, re-
spectively. Although PU-GO/FC-40 was ignited in the vertical burning
test, it only burned briefly. Surprisingly, the flame on it even self-ex-
tinguished before the fire source was removed.
The outstanding fire protection property of the GO/FC nanocoating
was attributed to its exceptional barrier effect to gases and heat. The
H. Xie, et al. Chemical Engineering Journal 369 (2019) 8–17

Table 2 nanosheets catalyzed the dehydration and carbonization reactions of

The effect of the coatings on the flame retardancy of PP, wood and PU foam. FC, leading to its efficient carbonization in the layered spaces of GO
Samples LOI Vertical burning test Horizontal burning test nanosheets. The carbonization products of FC bonded the graphene
nanosheets together (Fig. 3f and h). Meanwhile, the gaseous products of
PP 18.0 NR FH-3-26 mm/min FC made the hierarchical structure expanded. Therefore, hierarchical
PP-GO 19.5 NR FH-3-24 mm/min
porous char layer was formed and effectively insulated the substrates
PP/FC 19.0 NR FH-3-23 mm/min
PP-GO/FC-20 26.5 NR FH-3-18 mm/min
from heat and oxygen. These were also proved by the TG-FTIR results. It
PP-GO/FC-30 29.5 V-1 FH-3-15 mm/min was found from Fig. S8 that the degradation products of PP were mainly
PP-GO/FC-40 31.0 V-0 FH-1 hydrocarbons (especially methane (CH4)), carbon dioxide and water
PP-GO/FC-50 30.0 V-0 FH-1 vapour. After coated by GO/FC-40, the CH4 release amount of PP in TG-
PP-GO/FC-60 28.5 V-0 FH-1
FTIR was decreased by 25%, indicating that GO/FC-40 exhibited ex-
Wood 26.5 NR FH-4-51 mm/min
Wood-GO 28.5 NR FH-4-45 mm/min ceptional barrier effect and significantly decreased the degradation of
Wood/FC 29.0 NR FH-3-37 mm/min PP matrix. Moreover, it was observed from Fig. 4a2 and b2 that the
Wood-GO/FC-20 34.0 V-1 FH-2-32 mm skeleton of PU-GO/FC-40 was protected well and remained intact after
Wood-GO/FC-30 37.5 V-0 FH-1
burning. It was found that the carbon content of PU-GO/FC-40 did not
Wood-GO/FC-40 41.5 V-0 FH-1
Wood-GO/FC-50 40.0 V-0 FH-1
decreased but increased from 66.6% to 74.2%, and the oxygen content
Wood-GO/FC-60 37.5 V-0 FH-1 was decreased from 31.7% to 23.6% after burning. The results were
PU 17.5 NR FH-4-188 mm/min contradictory with those of the reported flame retardant polymers
PU-GO 18.0 NR FH-4-172 mm/min [32,38]. This was because the GO nanosheets were reduced to graphene
PU/FC 18.5 NR FH-4-147 mm/min
nanosheets in a high temperature environment; moreover, only part of
PU-GO/FC-20 20.0 V-2 FH-4-68 mm/min
PU-GO/FC-30 23.0 V-0 FH-3-33 mm/min the PU substrate underwent thermal degradation and thermal oxidation
PU-GO/FC-40 25.5 V-0 FH-2-31 mm due to the protective effect of GO/FC nanocoating.
PU-GO/FC-50 24.0 V-0 FH-2-47 mm
PU-GO/FC-60 23.0 V-0 FH-3-45 mm/min
3.4. Self-healing capability

The appearance of cracks on nanocoatings is unavoidable during

oxygen barrier test results in Table S1 showed that the oxygen per-
long-time use, because polymer coatings are prone to fatigue and
meability of GO/FC-40 was only 4.53 × 10−16 cm3·cm/(cm2·s·Pa),
damnification in particularly when they experienced repeated bending
which indicated that GO/FC-40 exhibited good barrier effect to oxygen
or other mechanical deformation. For GO/FC nanocoatings, cracks
[35,37]. Besides, when encountering fire, GO/FC nanocoating quickly
would cause deadly destruction to their conductive paths and char layer
formed hierarchical porous structure (Fig. 3f). In GO/FC nanocoating,
barriers, leading to the failure of their fire-warning response and fire
FC macromolecules were trapped in the closed layered spaces formed
protection effect. In order to evaluate the impact of the cracks on the
by GO nanosheets. When encountering fire, the acidic groups on GO
fire-warning response and fire protection effect of the GO/FC

Fig. 5. Vertical burning test processes of (a) PP and (b) PP-GO/FC-40. The results indicated that GO/FC nanocoating endowed PP with exceptional flame retardancy.

14
H. Xie, et al.
Fig. 6. (a) Mechanism of the moisture-triggered self-healing of GO/FC nanocoating. SEM images of the incisions on the surfaces of (b) GO/FC-20, (c) GO/FC-30, (d)
GO/FC-40, (e) GO/FC-50 and (f) GO/FC-60 before and after moisture-triggered self-healing. The results indicated that the existence of FC endowed GO/FC nano-
coatings with outstanding moisture-triggered self-healing capability.
nanocoatings, as shown in Fig. 6, the GO/FC nanocoatings on PP and
wood were cut by a blade, and incisions with a width of about 240 μm
were left on them. The damaged coated PP and wood could not trigger
the warning lamp in the fire-warning test (Figs. 7a and S10a) and they
were burned out in vertical burning test (Figs. 7c and S11a).
Fortunately, the existence of the FC molecular chains endowed GO/
FC nanocoatings with outstanding moisture-triggered self-healing cap-
ability. Fig. 6 shows that, after placed in the environment with a re-
lative humidity of 90% for 24 h and dried in air for 30 min, the incisions
on the nanocoatings were healed in different degree. When the FC
content in GO/FC system was larger than 70 wt%, the incisions on GO/
FC nanocoatings were healed completely. It was observed from Fig. 6b
and c that there was no any trace left on the surface of GO/FC-20 and
GO/FC-30 nanocoatings after moisture-triggered self-healing. This was
because the abundant UPy groups on FC chains formed multiple hy-
drogen bondings with each other or with the hydroxyl groups, epoxy
groups and carboxyl groups on GO nanosheets (Fig. 1b). In humid en-
vironment, water molecules untied parts of the original hydrogen
bondings by forming competitive hydrogen bondings with the above
groups [31,39], leading to the release and migration of the GO na-
nosheets and FC chains on the two sides of the incisions (Fig. 6a).
Therefore the incisions would be covered and healed through the re-
combination of the hydrogen bondings with the evaporation of the
water molecules. When the FC content in GO/FC system decreased to
60 wt%, the incision on the surface of GO/FC-40 nanocoating (Fig. 6d)
still self-healed successfully, although there was a faint trace left. With
the further decrease of the FC content, the traces left on the surfaces of
the GO/FC nanocoatings after moisture-triggered self-healing became
more and more obvious. When the FC content decreased to 40 wt%,
there were even fissures left on the trace (Fig. 6f). This was because on
the one hand, the migration of FC chains was much easier than that of
GO nanosheets; on the other hand, the binding force of the GO/FC
nanocoatings was mainly from the multiple hydrogen bondings formed
by the UPy groups. Therefore, the self-healing capability of the GO/FC
nanocoating would be weakened with the decrease of the FC content.
Besides, in order to investigate the maximum width of the incision
that could be healed on GO/FC nanocoating, incisions with different
width was created on GO/FC-40 and their self-healing test results were
shown in Fig. S9. It was found that when the width of the incision on
15
Chemical Engineering Journal 369 (2019) 8–17
GO/FC-40 was increased to about 320 μm, it still was healed sub-
stantially. However, when the width of the incision was further in-
creased to 380 μm, it was failed to be healed. Therefore, the maximum
width of the incision that could be healed for GO/FC-40 was about
320 μm.
Tables S2 and S3 shows the fire-warning time and the fire protection
effect of the healed nanocoatings on PP and wood, respectively. It was
found that the trigger time and fire protection effect of the healed GO/
FC nanocoatings recovered to their original level after self-healing. As
shown in Figs. 7b and S10b, the healed PP-GO/FC-40 and Wood-GO/
FC-40 triggered the warning lamp in 3.2 s and 3.4 s, respectively, in the
fire-warning test, which was close to their original fire-warning trigger
time (3.2 s and 2.9 s, respectively). Moreover, the healed PP-GO/FC-40
and Wood-GO/FC-40 both reached V-0 rating in the vertical burning
test and FH-1 rating in the horizontal burning test (Table S3). As shown
in Figs. 7d and S11b, PP-GO/FC-40 and Wood-GO/FC-40 self-ex-
tinguished in 3.4 s and 1.6 s, respectively, after the fire source was re-
moved in the vertical burning test.
In order to further evaluate the effect of the self-healing capability
of GO/FC nanocoating on the fire-warning response of the coated PU
foam, as shown in Fig. 7e, PU-GO/FC-40 was cut off into two parts and
the incision was moistened with water microdroplets. After pressed
together and dried in air for 30 min, the incision was healed in a certain
degree. Fig. 7f shows the fire-warning test process of the healed PU-GO/
FC-40. It was found that after encountered fire, the healed PU-GO/FC-
40 triggered the warning lamp in 3.4 s, which was only prolonged
slightly compared with that of the original PU-GO/FC-40 (2.4 s, Table 1
and Fig. S5b).
4. Conclusions
Based on functional cellulose (FC) and graphene oxide (GO), a
multifunctional flame retardant nanocoating was fabricated on com-
bustible materials (including polypropylene, polyurethane foam and
wood) via one-step self-assembly. The coated substrates exhibited ul-
trasensitive fire-warning response and exceptional fire safety. When
being attacked by fire at the very early stage, they rapidly triggered the
fire-warning less than three seconds. All the coated substrates were self-
extinguished in the vertical burning tests. Moreover, the nanocoating
H. Xie, et al.
Fig. 7. Fire warning test process of the (a) damaged and (b) healed PP-GO/FC-40. Vertical burning test of (c) damaged and (d) healed PP-GO/FC-40. (e) Treating
process of PU-GO/FC-40. (f) Fire warning test process of the healed PU-GO/FC-40. The results indicated that the fire-warning capability and flame retardancy of the
damaged PP-GO/FC-40 and PU-GO/FC-40 recovered to their original level after self-healing.
exhibited outstanding self-healing capability at room temperature. The
damaged nanocoating could be healed successfully and almost re-
covered to its original integrated performance. The nacre-like nano-
coating is promising for the application in fields of building, decoration,
transportation and electrical equipment, which remarkably decreases
the fire hazard of combustible materials.
Acknowledgments
We greatly acknowledge the National Natural Science Foundation of
China (51773064 and 51403067), the Natural Science Foundation of
Guangdong Province (2017A030313303), the Pearl River S&T Nova
Program of Guangzhou (201710010062), and the Fundamental
Research Funds for the Central Universities (2018MS04) for their fi-
nancial supports.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.03.045.
16
Chemical Engineering Journal 369 (2019) 8–17
References
[1] L. Xu, L. Xiao, P. Jia, K. Goossens, P. Liu, H. Li, C. Cheng, Y. Huang, C.W. Bielawski,
J. Geng, Lightweight and ultrastrong polymer foams with unusually superior flame
retardancy, ACS Appl. Mater. Interfaces 9 (2017) 26392–26399.
[2] P. Song, J. Dai, G. Chen, Y. Yu, Z. Fang, W. Lei, S. Fu, H. Wang, Z.G. Chen,
Bioinspired design of strong, tough and thermally stable polymeric materials via
nanoconfinement, ACS Nano 12 (2018) 9266–9278.
[3] Q. Wu, Q. Zhang, L. Zhao, S.N. Li, L.B. Wu, J.X. Jiang, L.C. Tang, A novel and facile
strategy for highly flame retardant polymer foam composite materials: transforming
silicone resin coating into silica self-extinguishing layer, J. Hazard. Mater. 336
(2017) 222–231.
[4] H. Xie, W. Yang, A.C.Y. Yuen, C. Xie, J. Xie, H. Lu, G.H. Yeoh, Study on flame
retarded flexible polyurethane foam/alumina aerogel composites with improved
fire safety, Chem. Eng. J. 311 (2017) 310–317.
[5] International Association of Fire and Rescue Services: World Fire Statistics. http://
www.ctif.org/.
[6] D.D. Evans, D.W. Stroup, Methods to calculate the response time of heat and smoke
detectors installed below large unobstructed ceilings, Fire Technol. 22 (1986)
54–65.
[7] J.R. Qualey, Fire test comparisons of smoke detector response times, Fire Technol.
36 (2000) 89–108.
[8] F. Pan, S.M. Chen, Y. Li, Z. Tao, J. Ye, K. Ni, H. Yu, B. Xiang, Y. Ren, F. Qin, S.H. Yu,
Y. Zhu, 3D graphene films enable simultaneously high sensitivity and large
stretchability for strain sensors, Adv. Funct. Mater. 28 (2018) 1803221.
[9] J. Liu, N. Wang, L.J. Yu, A. Karton, W. Li, W. Zhang, F. Guo, L. Hou, Q. Cheng,
L. Jiang, D.A. Weitz, Y. Zhao, Bioinspired graphene membrane with temperature
tunable channels for water gating and molecular separation, Nat. Commun. 8
(2017) 2011.
H. Xie, et al.
[10] Y. Fu, B. Jin, Q. Zhang, X. Zhan, F. Chen, pH-induced switchable superwettability of
efficient antibacterial fabrics for durable selective oil/water separation, ACS Appl.
Mater. Interfaces 9 (2017) 30161–30170.
[11] Y. Fu, J. Jiang, Q. Zhang, X. Zhan, F. Chen, Robust liquid-repellent coatings based
on polymer nanoparticles with excellent self-cleaning and antibacterial perfor-
mances, J. Mater. Chem. A 5 (2016) 275–284.
[12] Y. Zhang, P. Han, H. Zhou, N. Wu, Y. Wei, X. Yao, J. Zhou, Y. Song, Highly brilliant
noniridescent structural colors enabled by graphene nanosheets containing gra-
phene quantum dots, Funct. Mater. 28 (2018) 1802585.
[13] A.H. Gelebart, D. Liu, D.J. Mulder, K.H. Leunissen, J. van Gerven, A.P. Schenning,
D.J. Broer, Photoresponsive sponge-like coating for on-demand liquid release, Adv.
Funct. Mater. 28 (2018) 1705942.
[14] W. Wang, Y.Q. Liu, Y. Liu, B. Han, H. Wang, D.D. Han, J.N. Wang, Y.L. Zhang,
H.B. Sun, Direct laser writing of superhydrophobic PDMS elastomers for con-
trollable manipulation via marangoni effect, Adv. Funct. Mater. 27 (2017)
1702946.
[15] Q. Wu, L.X. Gong, Y. Li, C.F. Cao, L.C. Tang, L. Wu, L. Zhao, G.D. Zhang, S.N. Li,
J. Gao, Y. Li, Y.W. Mai, Efficient flame detection and early warning sensors on
combustible materials using hierarchical graphene oxide/silicone coatings, ACS
Nano 12 (2017) 416–424.
[16] Y. Du, W.Z. Qiu, Z.L. Wu, P.F. Ren, Q. Zheng, Z.K. Xu, Water-triggered self-healing
coatings of hydrogen-bonded complexes for high binding affinity and antioxidative
property, Adv. Mater. Interfaces 3 (2016) 1600167.
[17] M. Nakahata, S. Mori, Y. Takashima, H. Yamaguchi, A. Harada, Self-healing ma-
terials formed by cross-linked polyrotaxanes with reversible bonds, Chemistry 1
(2016) 766–775.
[18] X. Liu, C. Lu, X. Wu, X. Zhang, Self-healing strain sensors based on nanostructured
supramolecular conductive elastomers, J. Mater. Chem. A 5 (2017) 9824–9832.
[19] J. Kang, D. Son, G.J.N. Wang, Y. Liu, J. Lopez, Y. Kim, J.Y. Oh, T. Katsumata,
J. Mun, Y. Lee, L. Jin, J.B.H. Tok, Z. Bao, Tough and water-insensitive self-healing
elastomer for robust electronic skin, Adv. Mater. 30 (2018) 1706846.
[20] D. Son, J. Kang, O. Vardoulis, Y. Kim, N. Matsuhisa, J.Y. Oh, J.W.F. To, J. Mun,
T. Katsumata, Y. Liu, A.F. McGuire, M. Krason, F. Molina-Lopez, J. Ham, U. Kraft,
Y. Lee, Y. Yun, J.B.H. Tok, Z. Bao, An integrated self-healable electronic skin system
fabricated via dynamic reconstruction of a nanostructured conducting network,
Nat. Nanotechnol. 13 (2018) 1057–1065.
[21] J. Sun, X. Pu, M. Liu, A. Yu, C. Du, J. Zhai, W. Hu, Z.L. Wang, Self-healable,
stretchable, transparent triboelectric nanogenerators as soft power sources, ACS
Nano 12 (2018) 6147–6155.
[22] H. Ur Rehman, Y. Chen, M.S. Hedenqvist, H. Li, W. Xue, Y. Guo, Y. Guo, H. Duan,
H. Liu, Self-healing shape memory pupcl copolymer with high cycle life, Adv. Funct.
Mater. 28 (2018) 1704109.
[23] Y. Lai, X. Kuang, P. Zhu, M. Huang, X. Dong, D. Wang, Colorless, transparent, ro-
bust, and fast scratch-self-healing elastomers via a phase-locked dynamic bonds
design, Adv. Mater. 30 (2018) 1802556.
[24] Z. Wei, J.H. Yang, Z.Q. Liu, F. Xu, J.X. Zhou, M. Zrínyi, Y. Osada, Y.M. Chen, Novel
biocompatible polysaccharide-based self-healing hydrogel, Adv. Funct. Mater. 25
(2015) 1352–1359.
17
Chemical Engineering Journal 369 (2019) 8–17
[25] J. Qu, X. Zhao, Y. Liang, T. Zhang, P.X. Ma, B. Guo, Antibacterial adhesive in-
jectable hydrogels with rapid self-healing, extensibility and compressibility as
wound dressing for joints skin wound healing, Biomaterials 183 (2018) 185–199.
[26] M. Liu, P. Liu, G. Lu, Z. Xu, X. Yao, Multiphase-assembly of siloxane oligomers with
improved mechanical strength and water-enhanced healing, Angew. Chem. Int. Ed.
130 (2018) 11412–11416.
[27] L. Wang, Z.L. Gong, S.Y. Li, W. Hong, Y.W. Zhong, D. Wang, L.J. Wan, Molecular
conductance through a quadruple-hydrogen-bond-bridged supramolecular junction,
Angew. Chem. Int. Ed. 55 (2016) 12393–12397.
[28] X. Wang, Y. Li, Y. Qian, H. Qi, J. Li, J. Sun, Mechanically robust atomic oxygen-
resistant coatings capable of autonomously healing damage in low earth orbit space
environment, Adv. Mater. 30 (2018) 1803854.
[29] X. Yan, Z. Liu, Q. Zhang, J. Lopez, H. Wang, H.C. Wu, S. Niu, H. Yan, S. Wang,
T. Lei, J. Li, D. Qi, P. Huang, J. Huang, Y. Zhang, Y. Wang, G. Li, J.B.H. Tok,
X. Chen, Z. Bao, Quadruple H-bonding cross-linked supramolecular polymeric
materials as substrates for stretchable, antitearing, and self-healable thin film
electrodes, J. Am. Chem. Soc. 140 (2018) 5280–5289.
[30] G. Zhang, Y. Chen, Y. Deng, T. Ngai, C. Wang, Dynamic supramolecular hydrogels:
regulating hydrogel properties through self-complementary quadruple hydrogen
bonds and thermo-switch, ACS Macro Lett. 6 (2017) 641–646.
[31] Y. Chen, W. Cheng, L. Teng, M. Jin, B. Lu, L. Ren, Y. Wang, Graphene oxide hybrid
supramolecular hydrogels with self-healable, bioadhesive and stimuli-responsive
properties and drug delivery application, Macromol. Mater. Eng. 303 (2018)
1700660.
[32] H. Xie, X. Lai, H. Li, X. Zeng, Fabrication of ZrP nanosheet decorated macro-
molecular charring agent and its efficient synergism with ammonium polypho-
sphate in flame-retarding polypropylene, Compos. Part A-Appl. Sci. Manuf. 105
(2018) 223–234.
[33] L. Zhang, H. Li, X. Lai, X. Su, T. Liang, X. Zeng, Thiolated graphene-based super-
hydrophobic sponges for oil-water separation, Chem. Eng. J. 316 (2017) 736–743.
[34] G. Zhang, L. Lv, Y. Deng, C. Wang, Self-healing gelatin hydrogels cross-linked by
combining multiple hydrogen bonding and ionic coordination, Macromol. Rapid
Commun. 38 (2017) 1700018.
[35] F. Ding, J. Liu, S. Zeng, Y. Xia, K.M. Wells, M.P. Nieh, L. Sun, Biomimetic nano-
coatings with exceptional mechanical, barrier, and flame-retardant properties from
large-scale one-step coassembly, Sci. Adv. 3 (2017) e1701212.
[36] F.F. Chen, Y.J. Zhu, F. Chen, L.Y. Dong, R.L. Yang, Z.C. Xiong, Fire alarm wallpaper
based on fire-resistant hydroxyapatite nanowire inorganic paper and graphene
oxide thermosensitive sensor, ACS Nano 12 (2018) 3159–3171.
[37] J.N. Gavgani, H. Adelnia, M.M. Gudarzi, Intumescent flame retardant poly-
urethane/reduced graphene oxide composites with improved mechanical, thermal,
and barrier properties, J. Mater. Sci. 49 (2014) 243–254.
[38] X. Qiu, Z. Li, X. Li, Z. Zhang, Flame retardant coatings prepared by layer by layer
assembly: a review, Chem. Eng. J. 334 (2018) 108–122.
[39] H. Cheng, Y. Huang, Q. Cheng, G. Shi, L. Jiang, L. Qu, Self-healing graphene oxide
based functional architectures triggered by moisture, Adv. Funct. Mater. 27 (2017)
1703096.