Article

Cite This: ACS Nano 2018, 12, 416−424 www.acsnano.org

Efficient Flame Detection and Early Warning

Sensors on Combustible Materials Using
Hierarchical Graphene Oxide/Silicone Coatings
Qian Wu,† Li-Xiu Gong,† Yang Li,† Cheng-Fei Cao,† Long-Cheng Tang,*,†,⊥ Lianbin Wu,† Li Zhao,†
Guo-Dong Zhang,† Shi-Neng Li,†,‡ Jiefeng Gao,§ Yongjin Li,† and Yiu-Wing Mai*,⊥
†
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, College of Material, Chemistry and
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Chemical Engineering, Hangzhou Normal University, Hangzhou 311121, China

‡
Institute for Advanced Ceramics, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology,
Harbin 150001, China
§
College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, China
⊥
Centre for Advanced Materials Technology (CAMT), School of Aerospace, Mechanical and Mechatronic Engineering J07, The
University of Sydney, Sydney, NSW 2006, Australia
*
S Supporting Information

ABSTRACT: Design and development of smart sensors for

rapid flame detection in postcombustion and early fire
warning in precombustion situations are critically needed to
improve the fire safety of combustible materials in many
applications. Herein, we describe the fabrication of
hierarchical coatings created by assembling a multilayered
graphene oxide (GO)/silicone structure onto different
combustible substrate materials. The resulting coatings
exhibit distinct temperature-responsive electrical resistance
change as efficient early warning sensors for detecting
abnormal high environmental temperature, thus enabling
fire prevention below the ignition temperature of combustible materials. After encountering a flame attack, we demonstrate
extremely rapid flame detection response in 2−3 s and excellent flame self-extinguishing retardancy for the multilayered
GO/silicone structure that can be synergistically transformed to a multiscale graphene/nanosilica protection layer. The
hierarchical coatings developed are promising for fire prevention and protection applications in various critical fire risk and
related perilous circumstances.
KEYWORDS: hierarchical coatings, graphene oxide, silicone, flame detecting/warning sensor, temperature-responsive resistance change,
synergistic flame retardancy

inducing rapid temperature rise as an effective heat flux in the

T he deaths of about seventy-nine people in London’s

Grenfell Tower fire that occurred midnight on June 14,
2017, have focused much attention on the high risks
and rapid spreading of fire for many different combustible
materials. The flammability of the combustible materials, such
as polymer foams, woods, and textiles, has initiated massive fire
accidents which cause not only considerable property loss and
medical costs worldwide every year1 but also detrimental
impact on the surrounding environment and global climate.2,3
Triggered by an ignition source (flame, cigarette, glow wire,
etc.) in the range of ignition temperatures (600−700 K), the
endothermic pyrolysis of the combustible materials releases the
vaporization of decomposed products due to chain scission
mechanisms,4 resulting in CO and smoke production during
incomplete combustion.5 Meanwhile, a constant mass flux of
combustible volatiles feeds the exothermic reaction,6 thus
flame zone. These related fire issues drive the development of
fire safety strategy that can reduce fire risk to save lives and
protect properties.
For such purposes, two main fire detection strategies
including smoke detectors and infrared heat detectors have
been designed and installed indoor to monitor the high fire risk
of the combustible materials. Normally, these detectors are
activated through detecting the smoke product of a fire source
after the continuation of flaming combustion of the
combustible materials, thus showing a relatively long response
Received: September 16, 2017
Accepted: December 14, 2017
Published: December 14, 2017

© 2017 American Chemical Society 416 DOI: 10.1021/acsnano.7b06590

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Figure 1. Fabrication of hierarchical GO/silicone coatings on combustible materials. (a) Schematic illustration of fabricating hierarchical GO/
silicone coatings as efficient flame detection and early warning sensors on combustible materials. (b) Photographs of PU foam and PU-SGF
samples and their water contact angles. (c−e) Scanning electron microscopy images of the PU-SGF sample coated with the multilayered GO/
silicone structure. Surface treatment of PFDTS molecules onto GO sheets provides a hydrophobic surface and a protective layer that stabilizes
the GO network. (f) Photographs of the hierarchical coatings on various combustible materials: (i) polystyrene resin (PR), (ii) cotton (CN),
and (iii) wood block (WB).

time of >100 s.7,8 However, the combustible materials usually
burn rapidly once ignited, and the flame spreads very quickly
(e.g., >8 m flame height in only ∼80 s in a large-scale warehouse
fire test),9 potentially causing fatal burns within 15 s of
ignition,10,11 especially in oxygen-rich surroundings.12 The
main drawback of these two types of detectors is that they are
triggered in postcombustion and thus protractedly reflect the
fire behaviors of materials, which cannot offer a timely and
effective alarm signal to reduce or avoid the life and property
loss in fire accidents. Therefore, a critical challenge is to
develop efficient fire detecting/warning sensors that can trigger
rapidly and reliably real-time signals once the combustible
materials are attacked by a flame or even activate early warning
signals in precombustion when they are encountering high fire
risk, such as heat flux or abnormal high temperature for
ignition. Advanced multifunctional sensors that can meet the
requirement of extraordinary rapid and reliable responses for
detecting high fire risk of combustible materials are strongly
needed.
Herein, we describe a feasible method for fabricating
hierarchical coatings onto combustible materials as efficient
detecting/warning sensors including rapid flame detection in
postcombustion and early fire warning in precombustion. The
417
fabrication process uses a multilayered graphene oxide (GO)/
silicone structure that is assembled onto the combustible
substrates (see schematic representation in Figure 1a). Through
a simple dip-coating-induced assembly process (Figure S1 in
Supporting Information (SI)), a synthesized silicone polymer
(SiP) with predesigned three-dimensional cross-linked molec-
ular structure and GO sheets with lateral size ranging from 1 to
10 μm (Figure S2 in SI) are successively coated onto the
substrate surface. Then, 1,1,2,2-tetrahydroperfluorodecyltri-
methoxysilane (PFDTS) molecules are grafted onto the sheets
to obtain the hierarchical GO/silicone coatings on the
combustible substrate with a hydrophobic surface. The
optimized hierarchical coatings exhibit extraordinary rapid
flame detection response time of less than 3 s and outstanding
early warning for abnormal high temperatures that are below
the ignition temperature of the combustible materials and
excellent self-extinguishing flame-retardant property. To the
best of our knowledge, this is the most effective flame detection
response in postcombustion and the most efficient early flame
warning sensor in precombustion. This finding provides a
promising way for the development of advanced materials for
fire safety application of combustible materials.
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Figure 2. Rapid flame detection process of hierarchical GO/silicone coatings. (a,b) Flame detection processes of PU-SGF samples under
different environmental conditions. Alarm device system was established by connecting the sample with an alarm lamp and a low-voltage DC
power electrical source. Danger alarm was quickly triggered in 2−3 s once the sample encountered a flame, and continuous alarm was kept
even after removing the flame. Almost the same rapid response of flame detection alarm of PU-SGF was retained even after dropping some
water droplets (simulating a rainy day). (c) Electrical resistance change of PU-SGF samples before/after cyclic compression test during the
flame detection process. After 120 compression cycles, the sample showed unchanged response time for flame detection by measuring the
dramatic change in electrical resistance. Inset: PU-SGF sample recovered the original shape after applying a compressive strain of 75%. (d)
Electrical resistance change during the flame detection process for other combustible substrate materials (PR-SGF, CN-SGF, and WB-SGF).
Inset: Flame detection response time of all four samples was less than 3 s.

RESULTS AND DISCUSSION
The photographs of commercial polyurethane (PU) foam and
multilayered SiP/GO/PFDTS-coated PU (PU-SGF) samples
and the surface water contact angles (WCAs) are shown in
Figure 1b, in which the hierarchical GO/silicone coatings with
0.9/1.8/0.1/0.05 of PU/SiP/GO/PFDTS at the optimized
weight ratio (Figure S3 in SI) produce excellent super-
hydrophobicity of ∼156° WCA for PU-SGF compared to
∼88° WCA for pure PU foam. The organic−inorganic silicone
prepolymer synthesized by hydrolysis and condensation of
silane molecules can provide a large number of silanol groups,
which are expected to react covalently with the residual
isocyanate groups on the PU foam and the hydroxyl groups of
GO sheets.13 The PFDTS molecules after hydrolysis can react
with the GO sheets and SiP at a low temperature of 80−100
°C,14 thus forming a stable multilayered structure even after
being squeezed into an acidic or alkaline solution for 15 days
(Figure S4 in SI). We used thermogravimetric analysis (Figure
S5 in SI), Fourier transform infrared (FTIR) spectroscopy
(Figure S6 in SI), and X-ray photoelectron spectroscopy (XPS)
(Figure S7 in SI) to analyze different coatings of SiP, GO, SiP/
GO, and SiP/GO/PFDTS on the PU foam surface. The
characteristic curves and peaks of various materials including
PU, SiP-coated PU (PU-S), GO-coated PU (PU-G), SiP/GO-
coated PU (PU-SG), and PU-SGF samples show the expected
results for improved thermal stability and confirm the above
proposed reaction mechanisms.
418
The scanning electron microscopy (SEM) images of the
hierarchical GO/silicone coatings on the skeleton of PU foam
are shown in Figure 1c−e. The presence of the multilayered
SiP/GO/PFDTS structure does not affect the porous structure
of the foam significantly (Figure 1c) and produces a rougher
surface on the skeleton surface (Figure 1d) compared to the
smooth surface of the PU-G sample (Figure S8 in SI). The
cross-sectional SEM image of PU-SGF in Figure 1e shows a
typical 600−800 nm thick multilayered structure of the SiP
layer, interconnected GO layer, and a thin hydrophobic surface
which are well attached onto the PU skeleton. Such
multilayered structure can accommodate a large compressive
strain of 75% for 120 cycles, yet recovering its original shape
and size, indicating good structural stability, although the
maximum compressive stress does exhibit a reduction from
∼150 kPa for the first cycle to ∼92 kPa for the 120th cycle
(Figure S9 in SI). SEM-EDX mapping results (Figure S10 in
SI) of the sample reveal the appearance of well-distributed
silicon and fluorine elements on the rough surface, demonstrat-
ing the PFDTS molecules have been well grafted onto the
sheets, 15 which supports the superhydrophobic surface
obtained in Figure 1b due to the highly textured (rough
surface in Figure 1d) combined with the extremely low water
affinity.16 In fact, this multilayered coating method can also be
applied on various combustible substrate materials such as
polystyrene resin (PR), cotton (CN), and wood block (WB)
(Figure 1f), and obviously improved surface hydrophobicity on
these substrates (Figure S11 in SI) can be achieved. For a
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Figure 3. Early fire warning response of hierarchical GO/silicone coatings. (a) Abnormal high temperature early warning of the PU-SGF
sample in precombustion. Danger alarm was triggered in 20 s at 350 °C, and continuous alarm was kept even after leaving the hot surface,
indicating a good early warning for high fire risk. (b) Electrical resistance change of PU-SGF as a function of time at different temperatures.
Inset is a schematic of monitoring the resistance change at different environmental temperatures below the ignition temperature of the
combustible materials. (c) Alarm response time of the coatings at different temperatures. Inset: Raman spectra of PU-SGF under room
temperature (trace i) and 400 °C (trace ii), indicating thermal reduction of GO sheets. (d) SEM images of surface morphologies of PU-SGF
samples under different temperatures after 200 s: (i) 300 °C, (ii) 350 °C, and (iii) 400 °C. The decomposition of silicone at high temperatures
induced the microcracks and produced the porous nanosilica structure.

concise and clear analysis, representative GO/silicone-coated
PU samples will be mainly observed and discussed below with
respect to their structure and property measurements.
Well-exfoliated GO sheets in liquid solution can be easily
processed into a range of structures for diverse applica-
tions.17−19 Typically, GO-coated polymer sponge via a facile
dip-coating method produces a stable and thin conductive
graphene layer on the foam skeleton after chemical reduction,20
showing potential multifunctional applications in strain sensing,
oil/water separation, etc.21,22 However, for these graphene-
based materials, an additional fire retardant component is
required to achieve efficient fire resistance because the
graphene sheets tend to be completely burnt in air
atmosphere.23,24 Shown in Figure S12a and Movie S1
(Supporting Information) is the burning process of the GO-
coated PU (PU-G) sample, which is readily and completely
burnt in 30 s due to sufficient thermal degradation.
Comparatively, flame attack does not destroy the shape of
the PU-SGF sample even burned for ∼90 s (Figure S12b and
Movie S2 in SI), indicating the multilayered GO/silicone
structure protects the combustible PU foam from fire. In fact,
the SiP shows intrinsic flame retardancy,25 which is different
from the combustible linear silicone elastomers that inorganic
mineral fillers are usually needed as ceramization agents to
improve their flame resistance.26 We further compare the
structural stability of the PU-G and PU-SGF samples before
419
and after 10 s burning (Figure S13 in SI). Although they can
endure an applied weight of 200 g, their structural stabilities
after the burning tests are quite different. The PU-G sample
after burning is unstable and collapses easily, while the burnt
PU-SGF sample exhibits excellent structural stability, which can
be used to connect directly with the alarm lamp as an efficient
flame detection sensor.
The hierarchical GO/silicone coatings provide extremely
rapid responses for detecting flame on various combustible
substrates such as PU foam, polymer resin, cotton, and wood
block when connected with an alarm lamp and a low-voltage
DC power electrical source. As shown in Figure 2a, once the
PU-SGF sample encounters a flame, the danger alarm is quickly
triggered in 2−3 s, and a continuous danger alarm is maintained
even after removing the flame (Movie S3 in SI). Note that
almost the same response time of danger alarm is retained even
after dripping some water droplets onto the sample (simulating
a rainy day) (Figure 2b and Movie S4 in SI) or exposing it
outdoor for 180 days, indicating the good applicability in an
adverse environment. Further flame detection tests of the
hierarchical GO/silicone coatings on other combustible
substrate materials are shown in Figure S14 in SI. Similar
rapid responses (less than 3 s) of flame detection alarm can also
be triggered for PR (Movie S5 in SI), CN (Movie S6 in SI),
and WB (Movie S7 in SI). These tests indicate that the
hierarchical GO/silicone coatings show promising flame
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Figure 4. Flame-resistant properties and mechanisms of hierarchical GO/silicone coatings on combustible substrate materials. (a) Vertical
burning test (UL94) of a PU-SGF sample. The images show the sample before the test, after applying an alcohol flame for 10 s, and the sample
after the test, demonstrating excellent self-extinguishing characteristics and high fire retardancy. (b) Photographs of pure PU and PU-SGF
char after the cone calorimetry test together with the corresponding peak heat release rates (pHRR). The results reveal high fire resistance
and char for the hierarchical coatings on the PU foam. (c) Infrared spectra and corresponding photograph of a PU-SGF sample after burning
observed at different zones. (d) SEM images of the PU-SGF sample after burning. (e) Schematic illustration of the burning process of
multilayered GO/silicone structure on the PU skeleton (not drawn to scale). Both silicone decomposition and GO graphitization during the
burning process induce the formation of a multiscale nanosilica/RGO protective crust, which inhibits the pyrolytic degradation of the inside
RGO network, providing efficient flame detection and synergistic flame-retardant effect on the combustible substrate materials.

detection sensors for fire safety application in a building, which
is proposed and illustrated in Figure S15 in SI. Once a fire
originated from the lower floors spreads quickly to the higher
floors through combustible materials, such as the exterior wall
with combustible foam material, the hierarchical GO/silicone
coatings that are located in the high fire risk zone can provide a
rapid flame detection alarm for people living in the higher
floors to receive sufficient and timely notification for
evacuation. We believe the idea of a “rapid flame detection”
sensor can be simply, flexibly, and robustly used in large-scale
industrial applications where there are high fire risks which
should be critically monitored.
The explanation for this rapid response behavior for
detecting a flame lies in the change in the electrical resistance
of the multilayered GO/silicone structure, which comes from
the thermal reduction of the GO layer during the flame
attacking process (discussed later). As shown in Figure 2c, the
electrical resistance of the PU-SGF sample before/after 120
cyclic compressions under an applied strain of 75% (see insets
in figure) exhibits similar dramatic change in the burning
process with almost the same flame detection response time
(Movie S8 in SI). These results show good reliability of the
hierarchical coatings as flame detection sensors, even after
420
suffering a large compressive strain. The PR-SGF, CN-SGF,
and WB-SGF samples in Figure 2d also display significant
change in electrical resistance during the flame detection
process. The alarm response times (defined as the time that can
light up the alarm lamp at a low voltage of 24 V, corresponding
to about 4 orders of magnitude decrease in electrical resistance)
of all four samples, are extremely rapid (less than 3 s; see inset
in Figure 2d), which is much less than the reported response
time of smoke and heat detectors.7,8 Thus, monitoring the
change of flame-induced electrical resistance of the hierarchical
coatings is clearly much more effective than detecting the
smoke product and heat flux of the traditional smoke/heat
detectors, hence providing an efficient strategy for rapid flame
detection.
Heretofore, we believe no reports have shown any early
flame warning in precombustion because before being ignited
the combustible materials hardly release smoke and heat to
trigger the traditional detectors. It is well-known that two key
factors (i.e., ignition temperature and ventilation (oxygen)
atmosphere) critically determine the onset of flame and fire
growth and continuation of the combustible materials.27
Consequently, monitoring the temperature around the
combustible materials (below their ignition temperature) is a
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promising and effective way to reduce high fire risk in some
applications, such as batteries and wires/cables in public
transportation. Interestingly, the hierarchical GO/silicone
coatings on combustible substrates are sensitive to the
environmental temperature. Shown in Figure 3a and Movie
S9 are the temperature detection process of the PU-SGF
sample. When the sample was put onto a hot surface of ∼350
°C, a danger alarm was triggered in ∼20 s and maintained for a
long time, indicating efficient early fire warning of the
hierarchical GO/silicone coatings in precombustion. A temper-
ature oven was used to further evaluate the electrical resistance
response of the coatings at different temperatures, as illustrated
in the inset in Figure 3b and Figure S16, and the electrical
resistance changes of the PU-SGF sample as a function of time
were also measured. It is observed that the change of the
electrical resistance of PU-SGF samples is strongly dependent
on the applied environmental temperature; the higher the
temperature, the quicker and larger change of the electrical
resistance. The response time (as defined before) of the
hierarchical coatings exhibits dramatic reduction with increasing
temperature, for example, from ∼415 s at 200 °C (Figure S17
in SI) to ∼38 s at ∼300 °C (Movie S10 in SI) and ∼3 s for 400
°C (comparable to the response time for flame detection; see
Figure 3c), showing excellent early fire warning for monitoring
high fire risk of combustible materials in precombustion.
The PFDTS molecules bonded on the GO sheets not only
generate a hydrophobic surface that obtains rapid flame
detection in both sunny and rainy days but also provide a
protective layer that stabilizes the GO network on the surface of
the combustible material. Upon encountering a high temper-
ature or flame, the decomposition of silicone molecules
(PFDTS and SiP) induces microcracks and then produces a
porous nanosilica structure as an effective protection layer
(Figures S18 and S19 in SI).25,28 It is noted that both the size of
nanosilica particles and the thickness of the protective layer
show distinct increases with increasing temperature (from 200
to 400 °C) (Figure 3d), and this layer inhibits effectively the
thermal degradation of the GO sheets and facilitates the
reduction of GO to reduced GO (RGO).29 The thermal
reduction can be confirmed by the decreased intensity ratio of
the D and G Raman bands of GO in the multilayered structure
at ∼1335 and ∼1580 cm−1 (see inset in Figure 3c and Figure
S20a in SI), respectively,30,31 which is consistent with the
chemical transformations of organic silicone molecules in an
inorganic nanosilica porous protection layer (see FTIR results
in Figure S20b in SI).28 Meanwhile, the graphitization and
reduction of the GO sheets construct an effective conductive
network for rapid flame detection and early warning.
The formation of an environmentally friendly inorganic
nanosilica/RGO layer also improves significantly the fire
resistance of the combustible substrate materials, which is
quite different from the traditional flame retardants that are
halogenated or phosphorus compounds with negative impacts
on the environment and health.32,33 Vertical burning tests (UL
94) disclose that the uncoated PU foam combustible material
can be easily ignited (exposing the sample in a flame for only 1
s) and completely burnt in several seconds, accompanied by
continuous dripping and quick flame self-propagation (Figure
S21a and Movie S11).34 PU foams coated with GO or SiP (PU-
G or PU-S) display some flame retardancy but still burn for a
long time until they are completely combusted (Figure S21b
and Movie S1 for PU-G and Figure S21c and Movie S12 for
PU-S). Comparatively, the presence of hierarchical GO/silicone
421
Article
coatings produces excellent self-extinguishing fire resistance (in
20 s) without dripping and self-propagating flame phenomena
(Figure 4a and Movie S13 in SI). Similar self-extinguishing fire
resistance can be also observed for other combustible materials
including PR-SGF (Figure S22 and Movie S14), CN-SGF
(Figure S23 and Movie S15), and WB-SGF (Figure S24 and
Movie S16). Moreover, cone calorimetry tests demonstrate
that, after being exposed to a fixed heat flux of 35 kWm−2, the
char of the PU-SGF sample shows almost unchanged shape and
gray color in comparison with no char for the pure PU foam
(Figure 4b). The peak heat release rate (pHRR) of the PU-SGF
sample further displays obvious decrease (∼78%) compared to
that of pure foam and is much lower than those of the PU-G
and PU-S samples (Figure 25a in SI), albeit the weight loss
ratio of the PU-S sample is almost the same as that of the PU-
SGF sample (Figure S25b in SI).
To understand the flame-retardant mechanisms of the
hierarchical GO/silicone coatings on combustible substrate
materials, the PU-SGF sample after the burning test was
observed and analyzed. Figure 4c shows that the multilayered
GO/silicone structure is transformed into an inorganic
protective layer in the outside zone during the burning process,
similar to cellulose nanofibers/GO/sepiolite nanorod nano-
composite foams35 and Al2O3 nanolayer-coated graphene
sandwiched structure,36 which can be confirmed by the FTIR
results. The intense Si−O−Si band at ∼1038 cm−1 in the
outside surface zone and many peaks of massive organic groups
in the inside zone (O−H band at 3342 cm−1, C−H band at
2960 and 2860 cm−1, CC band at 1720 cm−1, C−C band at
1597 cm−1, Si−C band at 1265 and 783 cm−1, Si−O−C band at
1088 cm−1, and Si−O−Si band at 1597 cm−1) indicate that the
protective silica-rich surface layer inhibits effectively the thermal
degradation of the inside GO/silicone coating. The decreased
intensity ratio of the D and G Raman bands of GO (ID/IG)
after burning (Figure S20a in SI) suggests a reduction of GO to
RGO in the flame37 and transformation of GO sheets into
char.38
SEM images in Figure 4d demonstrate that the porous
nanosilica protective crust is formed on the RGO network in
the outside zone, and the hierarchical GO/silicone structure in
the inside zone does not show obvious thermal decomposition
(Figure S26 in SI). Once encountering an abnormal high
temperature or flame attack, thermal degradation of surface
PFDTS molecules transforms into a nanosilica protective layer
to inhibit the decomposition of GO sheets but rapidly reduces
them for efficient fire detection and early warning. For a
continuous flame, the inside SiP polymer would decompose
through the microcracks on the surface (as shown in Figure 3d)
to form the porous nanosilica layer. As a result, the formation of
multiscale porous nanosilica and RGO char as an effective
protective layer can synergistically suppress the transport of
heat and oxygen (Figure 4e),39,40 thus showing an “environ-
mentally f riendly” alternative for protecting foams and many
other complex substrates (e.g., fabrics) without altering their
processing and desirable mechanical behavior.41 Indeed,
analysis of the chemical and structural transformations of
hierarchical GO/silicone coatings shows that the porous
nanosilica structure produced by the silicone polymer at the
high temperature effectively suppresses the transport of heat
(Figure S27 in SI) and thus promotes the graphitization of GO
and the formation of the RGO conductive network (Figure S28
in SI), providing excellent flame retardancy and flame rapid
detection for the combustible substrate materials.
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CONCLUSIONS Electrical resistance of various samples was monitored with a two-

In summary, the hierarchical GO/silicone coatings show that an
extremely rapid response (less than 3 s) to flame detection and
an ideal early warning to the environmental temperature
(below ignition temperature of the combustible materials) in
precombustion and ease of applicability can be achieved by the
simple and feasible dip-coating method. Various potential fire
safety applications of the hierarchical GO/silicone coatings as
efficient flame detection and early fire warning sensors are
supported by our results through detecting temperature-
dependent electrical resistance change. The coatings can also
be readily implemented on different combustible substrate
materials where fire safety is critically required. In addition, the
porous nanosilica structures as an effective protective layer
electrode method (ESCORT 3146A multimeter), and each end of the
samples was carefully affixed to copper sheets as electrodes. A vertical
flame test was performed on uncoated and coated combustible
samples. The fire from a gas burner was applied on the tested fabric for
10 s and then removed, and before testing, the specimens were
conditioned at 25 ± 1 °C and 50 ± 2% relative humidity for 72 h. PU,
PU-G, PU-S, and PU-SGF samples were characterized using a cone
calorimeter performed in an FTT, UK device according to ISO 5660,
and samples with dimensions of 100 mm long × 100 mm wide × 10
mm thick were exposed to a heat flux of 35 kW m−2, and the data
reported in this work were the averages of three experiments.
ASSOCIATED CONTENT
*
S Supporting Information

transformed from silicone polymer during burning protect the The Supporting Information is available free of charge on the
degradation of GO from fire and promote the formation of a ACS Publications website at DOI: 10.1021/acsnano.7b06590.
RGO conductive network, thus yielding excellent flame Figures S1−S28 and captions for Movies S1−S16 that
retardancy. Our results provide substantial motivation and show structural characterizations of hierarchical coating,
opportunity to develop advanced multifunctional sensors for performance of the hierarchical coating on various
fire prevention and protection applications in buildings, combustible materials, demo movies of flame detect-
transportation, and public security where combustible materials ing/warning sensor and flame resistance, investigation on
are widely used. the working principle of the hierarchical coating and
experiment on synergistic flame-retardant effect (PDF)
METHODS Movie S1 (AVI)
Materials and Preparation. Materials and detailed synthesis of Movie S2 (AVI)
GO and silicone polymer are given in the Supporting Information. The
Movie S3 (AVI)
PU-SGF sample was prepared as follows. Synthesized silicone
prepolymer (50 g), alcohol (50 g), and polyetheramine D230 (0.6 Movie S4 (AVI)
g) were mixed at 1000 rpm for 20 min to obtain a homogeneous Movie S5 (AVI)
solution. Pure PU foam was then fully immersed into the above Movie S6 (AVI)
mixture under vacuum for 15 min and then centrifuged at 600 rpm for Movie S7 (AVI)
5 min to remove the extra silicone prepolymer. The sample was then Movie S8 (AVI)
cured by D230 at 90 °C for ∼4 h to obtain the PU-S sample. After
that, the PU-S sample was fully immersed into the GO aqueous Movie S9 (AVI)
solution aided by a vacuum pump and centrifugation and then dried at Movie S10 (AVI)
70 °C for 4 h to obtain the PU-SG sample. Finally, PFDTS (1 g) and Movie S11 (AVI)
DI water (0.5 mL) were dispersed in 250 mL of alcohol and Movie S12 (AVI)
ultrasonicated for 10 min, and then the above PU-SG sample was fully Movie S13 (AVI)
immersed into the above PFDTS mixture at 60 °C for 5 min and dried
at 70 °C for 2 h. Similarly, various combustible materials coated by the Movie S14 (AVI)
silicone polymer, GO, and silicone/GO were fabricated according to Movie S15 (AVI)
the above process. Further detailed information is provided in the Movie S16 (AVI)
Supporting Information.
Characterization. Raman spectra of various samples were
obtained from 200 to 4000 cm−1 using a SENTERRA micro-Raman
AUTHOR INFORMATION
spectrometer (Bruker Instruments, Germany) with a 633 nm He−Ne Corresponding Authors
laser beam. The morphology and structure of GO sheets were *E-mail: lctang@hznu.edu.cn.
analyzed by transmission electron microscopy (HITACHI H- 7650) *E-mail: yiu-wing.mai@sydney.edu.au.
and atomic force microscopy (Digital Instrument D3100). The surface
ORCID
morphologies of various samples before or after flame burning tests
were examined by scanning electron microscopy (Zeiss ultra plus and Long-Cheng Tang: 0000-0002-2382-8850
HITACHI S-4800) with an energy dispersive X-ray spectroscopy Yongjin Li: 0000-0001-6666-1336
detector. X-ray diffraction was performed using a diffraction Notes
technology mini-materials analyzer on the samples with a D/
The authors declare no competing financial interest.
Max2550 V X-ray diffractor (Rigaku, Japan), and the diffraction
patterns were recorded in the 2θ range from 5 to 40° with a scan rate
of 5° min−1. Fourier transform infrared spectra were obtained using a ACKNOWLEDGMENTS
Nicolet 7000 FTIR (Nicolet Instrument Company, USA) between 600 This work was supported by the National Natural Science
and 4000 cm−1. High-resolution XPS measurements were obtained Foundation of China (Grants 51203038 and 51403047), the
using the VG scientific ESCALab 220I-XL equipped with Mg Kα X-ray Zhejiang Provincial Natural Science Foundation (Grants
source and a hemispherical electron analyzer. Themogravimetric LY15E030015 and LY18E030005), and the Project for the
analysis was performed by a TA Instruments Q500 in air/nitrogen
atmospheres at a heating rate of 10 °C min−1 between room Innovation of High Level Returned Overseas Scholars in
temperature and 800 °C. Hangzhou. The authors thank Y. Wang, F. Qiang, and Y.J. Wan
Compression tests were performed using an AMETEK Ls 100Plus for AFM and SEM characterizations. The authors also thank
(100N load cell) at a speed of 1.0 mm/min at room temperature, and Dr. Y.B. Pei for discussions of possible fire-retardant
the samples size was 20.0 mm long × 20.0 mm wide × 10.0 mm thick. mechanisms.
422 DOI: 10.1021/acsnano.7b06590
ACS Nano 2018, 12, 416−424
ACS Nano
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424 DOI: 10.1021/acsnano.7b06590

ACS Nano 2018, 12, 416−424