Received: 5 December 2020 Revised: 14 January 2021 Accepted: 14 January 2021

DOI: 10.1002/pat.5231

RESEARCH ARTICLE

Flame-retardant cellulose nanofiber aerogel modified with

graphene oxide and sodium montmorillonite and its fire-alarm
application

Boyu Zuo | Bihe Yuan

School of Safety Science and Emergency

Management, Wuhan University of Thermal insulation materials (TIMs) are widely used to realize energy conservation in
Technology, Wuhan, China
buildings, but most of the commonly used organic TIMs are flammable. A novel
Correspondence biomass-based aerogel is produced by an environmentally friendly vacuum freeze-
Bihe Yuan, School of Safety Science and
drying method, and a facile approach is proposed to improve the flame-retardant per-
Emergency Management, Wuhan University of
Technology, Wuhan 430070, China. formance of cellulose nanofiber (CNF) aerogels by modifying them with graphene
Email: [email protected]
oxide (GO) and montmorillonite (MMT). GO and MMT form a barrier that blocks the
Funding information contact between the composite aerogel and the external oxygen, achieving the
National innovation and Entrepreneurship
flame-retardation effect. Notably, based on the high-temperature thermal reduction
Training Program for college students, Grant/
Award Number: 202010497001; National characteristic of GO, a fire-alarm system that can provide an ultrasensitive and reli-
Natural Science Foundation of China, Grant/
able fire-warning signal is designed. A fire alarm of CNF-MMT-GO-50% can be trig-
Award Number: 51703175
gered in approximately 1.9 seconds and lasts for more than 137.0 seconds when the
aerogels are attacked by fire. This work helps to develop advanced TIMs to solve the
shortcomings of traditional organic insulation materials and supplies a newfangled
idea for the design of fire-alarm sensors, showing promising applications in building
insulation, firefighting, and chemical industry.

KEYWORDS
cellulose nanofiber aerogel, fire-warning response, flame resistance, graphene oxide

1 | I N T RO DU CT I O N using hydrofluorocarbons, which are intense greenhouse gases. PS

insulation materials without fire-retardant treatment are hazardous in
Fire is one of the main causes of accidents that threaten public safety case of a fire. Inorganic TIMs are incombustible; however, they always
and social development. The use of thermal insulation materials consume a large amount of energy in the fabrication process and also
(TIMs) is the most effective way of realizing energy conservation in cause serious environmental pollution during the exploiting or smash-
1
buildings, and a large number of TIMs are used in these. However, ing process.4-7 Researchers have been exploring various methods and
these organic materials are widely used and easily ignited, thus technologies to reducing fire risk and loss, such as the use of flame-
increasing the casualties in building fires.2,3 In urban buildings, retardant and suppression technologies.8-12 Flame-retardant materials
because of the dense population and the use of building TIMs, a fire can effectively change passive to active fire prevention, restrain the
often causes serious damage. On June 14, 2017, a fire occurred in a fire spread in the initial stage, and thus reduce the fire risk.
24-story apartment building in west London, UK. Owing to the use of Biomass-based cellulosic aerogels not only possess some excel-
flammable TIMs on the exterior walls, the fire quickly spread to almost lent properties, such as low density, high specific surface area, and
all floors, leaving 79 dead. Organic TIMs have the advantages of light- high porosity, but also have the advantages of being natural, renew-
weight and low thermal conductivity. However, expanded polystyrene able, and degradable. They are widely used in sound insulation,
(EPS), extruded polystyrene (XPS), polyurethane (PU), and other adsorption, and other fields and also possess broad application pros-
organic TIMs are generally flammable. XPS is typically produced by pects in the field of TIMs.13-17 Cellulose aerogel is a kind of flammable

Polym Adv Technol. 2021;32:1877–1887. wileyonlinelibrary.com/journal/pat © 2021 John Wiley & Sons Ltd 1877
1878 ZUO AND YUAN

material, thus it is particularly important to design cellulose aerogel extremely fast flame detection response of only 1 seconds.42 Chen
with flame-retardant property to effectively prevent fire and reduce et al fabricated a flame-retardant paper based on GO and phytic acid.
18,19
the damage caused by fire. Han et al fabricated cellulose aerogels When this GO-phytic acid sample is attacked by fire, the alarm will be
from waste cotton fabrics and magnesium hydroxide nanoparticles, triggered in approximately 0.5 seconds.43
and the hybridized cellulose aerogels showed wonderful flame In this work, we prepared a cellulose nanofiber (CNF) aerogel by
retardancy.20 freeze-drying, and GO and Na-MMT were introduced to improve its
Montmorillonites (MMTs), such as sodium montmorillonite (Na- flame retardancy. Based on the thermal sensitive property of GO, we
MMT), have been widely used to improve polymers' flame-retardant designed a fire-alarm device based on this composite aerogel material.
property, and the flammability decreases with increasing amounts of This biomass-based flame-retardant aerogel material is not only a new
MMT.21-23 Na-MMT can promote the formation of a dense char layer type of environmentally friendly TIM but also can provide timely and
in the polymer and form a protective barrier to retard flame accurate fire early warning.
spread.24-26 Based on these characteristics of Na-MMT, many experts
have chosen Na-MMT as a flame retardant for aerogel materials.27-29
The research by Long et al showed that MMT is absorbed on the cel- 2 | EX PE RI MENT AL
lulose substrate surface via hydrogen bonding and is embedded in the
pore structure of the aerogel.30 Chen et al fabricated flame-retardant 2.1 | Materials
PU foams with alginate and MMT aerogel coatings.31 Wang et al used
MMT to prepare a variety of flame-retardant polymers such as polyvi- Graphite powder (granularity ≤30 μm, chemically pure) was provided
32,33
nyl alcohol and renewable xanthan gum. Wang et al constructed by Sinopharm Chemical Reagent Co., Ltd. GO slurry was produced
cellulose/MMT hydrogels prepared from a mixture of cellulose solu- from graphite powder using the Hummers method.44 CNF hydrogel
tion and MMT suspension. The results showed that the bioplastics (mass fraction: 1.27 wt%; carboxyl group content: 1.4 mmol g−1;
formed by adding MMT to cellulose exhibit excellent flame length: 1-5 μm; diameter: 10-20 nm) was provided from Tianjin
34
retardancy. Woodelf Biotechnology Co., Ltd. Na-MMT powder (density:
During fire incidents, a timely and reliable fire alarm plays an 1.02 g cm−3; purity ≥99%) was provided from Hebei Yanbo Mineral
important role in fire evacuation, so that people can get alarm infor- Processing Plant. The above reagents were used directly without fur-
mation at the beginning stage of fire and have enough time to evacu- ther purification.
ate or rescue. Smoke detectors and infrared detectors are the most
widely used traditional indoor fire-detection strategies. However, they
suffer from some defects. For example, infrared detectors are easily 2.2 | Preparation of CNF, CNF-MMT, and CNF-
affected by various heat sources and have poor penetration ability MMT-GO aerogels by vacuum freeze-drying method
during the smoke scenario. Furthermore, the use of smoke detectors
outdoors is limited, and the alarm can be activated only when the fire CNF, CNF-MMT, and CNF-MMT-GO aerogels were produced by vac-
lasts for a while and produces a lot of smoke. Thus, the response time uum freeze-drying, which is a simple and environmentally friendly
is relatively long, and it is easy to generate a false alarm.35-37 There is strategy to produce CNF aerogels.16 First, a certain amount of CNF
a necessity to devise a novel fire alarm with high efficiency and stable hydrogel was weighed in a beaker and stirred evenly. Then, GO sus-
performance. pension and Na-MMT powder were weighed and mixed with the CNF
Graphene has become increasingly important in the materials sci- hydrogel. An appropriate quantity of deionized water was added to
ence field since its discovery in 2004, and its unique physical and the beaker, which was followed by 15 minutes of ultrasonic mixing to
10
chemical properties have attracted extensive attention. As an prepare a homogeneous dispersion. Finally, the mixture was trans-
important derivative of graphene, graphene oxide (GO) is a new car- ferred to a mold to pre-freeze for 12 hours and then placed into a vac-
bon material with excellent physical properties and chemical struc- uum freeze dryer at −54 C for 48 hours to obtain the composite
tures. It has a high specific surface area and abundant surface aerogels. The composition and nomenclature of the aerogel samples
functional groups. Graphene exhibits excellent electrical conductivity, are shown in Table 1. CNF and CNF-MMT aerogel samples were pre-
which is due to its unique electronic structure. GO, as a chemically pared as control groups.
modified graphene, is electrically insulating. Under the action of high-
temperature, such as during a fire, GO is easily reduced and its
oxygen-containing groups are removed, restoring its conductive struc- 2.3 | Characterization
ture. The characteristics of GO resistance influenced by the tempera-
ture have been paid a lot of attention by researchers in the field of The structure and surface morphology of the aerogel samples were
fire sensors. Dr Yu (Xiamen University) and Dr Tang (Hangzhou Nor- observed by a JSM-IT300 scanning electron microscope (SEM) under
mal University) have employed this unique property of GO to devise 20 kV accelerating voltage.
fire- or high-temperature-warning sensors.38-41 Zhang et al prepared Thermogravimetric analysis (TGA) was carried out on a STA6000
a green flame-retardant GO-based paper/coating, which exhibited an simultaneous thermo-analyzer. The samples were heated from 30 C
ZUO AND YUAN 1879

to 700 C with a heating rate of 20 C min−1 under nitrogen gas at a Fourier transform infrared (FTIR) spectrum was obtained on an
flow rate of 20 ml min−1. intelligent Fourier transform infrared spectrometer (Thermo Nicolet)
X-ray diffraction (XRD) patterns were obtained using a D8 over the wavenumber range 4000 to 400 cm−1.

Advance X-ray diffractometer and recorded in the 2θ range of 5
to 60 .
The samples were placed on a J-104 heating table for thermal 3 | RESULTS AND DISCUSSION
insulation testing. A thermal infrared imager FLIR system was used to
shoot a 15-minutes video recording, and the data was processed by 3.1 | Structural characterizations of composite
the software of FLIR Tools. aerogels
Microscale combustion calorimetry (MCC) data was obtained
using an FAA micro calorimeter, and the heating rate was 1 C s−1 with In this work, CNF-MMT-GO-30% was chosen as the representative
a nitrogen flow rate of 80 ml min−1 and an O2 flow rate of sample for characterization. Figure 1A shows the preparation process
20 ml min−1. of CNF-MMT-GO aerogel by vacuum freeze-drying. The mixture of
The thermal conductivity of the aerogel samples was measured CNF, MMT, and GO was pre-frozen for 12 hours and placed into a
by the transient plane source method on a hot disk TPS2500S. vacuum freeze dryer for 48 hours to obtain the composite aerogel. As

TABLE 1 Composition and nomenclature of composite aerogel samples

Sample CNF hydrogel (g) GO slurry (g) Na-MMT (g)

CNF 31.493 (100%) 0 0
CNF-MMT 31.498 (80%) 0 0.101 (20%)
CNF-MMT-GO-30% 31.497 (50%) 14.765 (30%) 0.160 (20%)
CNF-MMT-GO-40% 31.495 (40%) 24.605 (40%) 0.200 (20%)
CNF-MMT-GO-50% 31.494 (30%) 41.033 (50%) 0.268 (20%)

Note: The mass fractions of CNF hydrogel and GO slurry are 1.27 and 1.6258 wt%, respectively.

F I G U R E 1 A, Schematic of the preparation of CNF-MMT-GO. The light aerogel samples are supported on setose asparagus. The compression
properties of, B, CNF, C, CNF-MMT, D, CNF-MMT-GO-30%, E, CNF-MMT-GO-40%, and F, CNF-MMT-GO-50%
1880 ZUO AND YUAN

F I G U R E 2 Thermal images of the top side of the aerogel samples on a 135 C hot plate: A, CNF, B, CNF-MMT, C, CNF-MMT-GO-30%, D,
CNF-MMT-GO-40%, and E, CNF-MMT-GO-50%

T A B L E 2 Thermal conductivities of CNF, CNF-MMT, and CNF- is similar to those of other samples, and the interconnected GO net-
MMT-GO-30% work is formed by the support of the skeleton of the CNF aerogel.48

Sample Thermal conductivity (mW mK−1)

These results suggest that the introduction of MMT and GO has little
influence on the original excellent porous structure of the CNF
CNF 40
aerogel.
CNF-MMT 39
CNF-MMT-GO-30% 39

3.2 | Flame resistance and thermal stability of the

composite aerogels
shown in Figure 1B-F, all the aerogels are lightweight. Therefore,
setose asparagus can support these aerogels. A weight is placed on To evaluate the effect of composited GO and MMT on the flame
the top of the composite aerogels to study their compression proper- resistance of CNF aerogels, the aerogel samples were combusted
ties. The deformation of these aerogels is not obvious under a com- using an alcohol lamp flame; the related combustion processes are
pression of 100 g weight. With the addition of MMT and GO, the shown in Figure 4A-E. The aerogel samples were burned on the flame
density of the composite aerogel also increases. of the alcohol lamp and removed after a 15-seconds fire exposure. As
To evaluate the thermal insulation performance, the aerogel's shown in Figure 4A, the CNF aerogel showed high flammability and
thermal images at different times were recorded (Figure 2). The point was completely burned out. As shown in Figure 4B-E, the flame resis-
at the top is chosen as a reference to show the time dependence of tance of CNF-MMT is significantly improved. With the addition of
the surface temperature of the aerogel. The temperature change after GO, more char residue is produced, and the original shape of aerogels
15-minutes heating is minor. Table 2 shows a thermal conductivity of is maintained after combustion. This result reveals that CNF-MMT-
−1 
39 mW mK at 25 C for CNF-MMT-GO-30%, indicating similar insu- GO exhibits much better flame resistance than CNF-MMT.
lating properties as those of traditional TIMs such as EPS The thermal stability of the aerogel samples was investigated by
(30-40 mW mK−1) and XPS (25-35 mW mK−1).45 This is attributed to TGA (Figure 5A) and differential thermogravimetry (DTG) (Figure 5B).
the high porosity of aerogels, which exhibit superb thermal insula- As shown in Figure 5A, the mass loss of CNF and CNF-MMT can be
46
tion. Table 2 shows that the thermal conductivity is insignificantly divided into two stages, whereas the other three samples containing
affected by the increased density of the composite aerogel. The com- GO and MMT correspond to three decomposition stages. The TGA
parison of the insulation performance with those of similar TIMs is curves indicate that all samples show a similar tend to release the
given in Table S1. absorbed water on heating from room temperature to approximately
Figure 3A shows the cross-sectional SEM images of CNF and 160 C. For the GO-based aerogels, the second main loss stage occurs
composite aerogels. When the frozen water is removed by sublima- at approximately 170 C to 250 C, which is attributed to the thermal
tion, CNF nanofibers are held together by van der Waals forces and removal of oxidized groups on GO.49 The final mass loss is caused by
hydrogen bonds. Thus, sheet-like morphology, sponge-like structure, the thermal decomposition reaction of CNF. The addition of the flame
47
and high porosity can be observed for CNF aerogel. As shown in retardant decreases the mass loss rate and increases the residual mass
Figure 3B, the granular Na-MMT is evenly distributed in the CNF fraction apparently, which can be explained by the barrier effects of
aerogel. As shown in Figure 3C, the structure of CNF-MMT-GO-30% MMT and GO.50 These results demonstrate that the thermal stability
ZUO AND YUAN 1881

FIGURE 3 Scanning electron microscope (SEM) images: A, CNF, B, CNF-MMT, and C, CNF-MMT-GO-30% aerogel

FIGURE 4 Combustion processes: A, CNF, B, CNF-MMT, C, CNF-MMT-GO-30%, D, CNF-MMT-GO-40%, and E, CNF-MMT-GO-50%

of CNF at high-temperature is significantly improved after the incor- heat and mass transfers, making the composite aerogel to have better
poration of MMT and GO. flame retardancy.51,52
MCC is used to investigate the heat release of the aerogel sam-
ples during the combustion of volatile products. The heat release rate
(HRR) curves are shown in Figure 6, and the parameters of peak heat 3.3 | Fire-warning response of composite aerogels
release rate (PHRR), total heat release (THR), and the temperature at
PHRR (TPHRR) are given in Table 3. As shown in Table 3 and Figure 6, The fire-alarm response of composite aerogels was explored. For this,
the PHRR and THR values of CNF-MMT-GO-30% (28.0 W g−1 and a testing circuit based on a low-voltage battery, an alarm lamp, multi-
−1
2.79 kJ g , respectively) are decreased compared with those of CNF ple wires, and the composite aerogels, as shown in Figure 7, was
(48.9 W g−1 and 4.43 kJ g−1, respectively). This indicates that the designed to study the sensitivity of the fire alarm. The composite
combustion of CNF releases a large amount of heat in a short time. aerogels show an ultrasensitive fire-warning response. The testing
With the addition of MMT and GO, the values of PHRR and THR videos are recorded in Movies S1 to S5, and the snapshots of fire-

decrease significantly. Furthermore, its TPHRR increased from 260.8 C alarm processes are shown in Figures 8 to 10. As shown in Movies S1
to 306.6 C. The improved flame retardancy is ascribed to a protective and S2, the aerogel samples in the absence of GO cannot realize the
layer formed from MMT and GO, which forms an excellent barrier for fire-alarm function.
1882 ZUO AND YUAN

FIGURE 5 A, Thermogravimetric analysis (TGA) and B, differential thermogravimetry (DTG) curves of aerogel samples in nitrogen atmosphere

With the increase in GO content, CNF-MMT-GO-40% shows a

superb fire-warning response. As shown in Figure 9 and Movie S4, an
ideal and rapid warning response can be triggered after confronting
an approximately 2.0 seconds fire attack, and the duration time is
enhanced to approximately 62.4 seconds.
Owing to the high concentrations of GO, the thermal reduction
reaction is violent and the fire-warning response of CNF-MMT-GO-
50% is triggered within 1.9 seconds of a fire attack, showing a more
sensitive response than previously reported GO/functional cellulose
nanocoatings (<3 seconds)53 and GO-based paper/coating at 300 C
(<7 seconds).42 The duration time is increased to 137.0 seconds, as
presented in Figure 10 and Movie S5. With the increase in GO con-
tent, the fire-warning of the resulting aerogels becomes more sensi-
tive and durable.
The above results indicate that the composite aerogels prepared
show a superior and sensitive fire-warning response, which is promis-

F I G U R E 6 Heat release rate (HRR) curves of aerogel samples ing to be applied in the new field of TIMs with fire sensing function.
during microscale combustion calorimetry (MCC) testing

3.4 | Flame-retardant and fire-warning

T A B L E 3 Combustion heat release data of CNF and CNF-MMT-
GO-30% from MCC tests
mechanisms of composite aerogels

Sample PHRR (W g−1) THR (kJ g−1) TPHRR ( C) Flame-retardant effect of aerogels is enhanced obviously by
CNF 48.9 4.43 260.8 nanofillers, and the aerogel with GO changes from insulation to con-
CNF-MMT-GO-30% 28.0 2.79 306.6 ductive, owing to the thermal reduction of GO by fire (see Data S1).

Abbreviations: MCC, microscale combustion calorimetry; PHRR, peak heat To investigate the flame-retardant and fire-warning mechanism of the
release rate; THR, total heat release. composite aerogels, XRD, SEM, and FTIR were used to analyze the
residual char. As shown in Figure 11A, the crystal structures of GO
and CNF-MMT-GO-30% before and after combustion were investi-
The flame-alarm detecting process of CNF-MMT-GO-30% is gated by XRD. The characteristic peak at 22.38 belongs to cellu-
presented in Figure 8 and Movie S3. The danger alarm can be trig- lose.54 The characteristic (002) diffraction peak of GO appears at
gered within 6.2 seconds after contacting with the flame and then the 10.18 . However, this characteristic peak is found at 7.81 in the XRD
signal continued for 63.1 seconds. Therefore, it does not supply a suf- pattern of CNF-MMT-GO-30%, suggesting the enhanced interlayer
ficiently prompt and sustainable alarm. spacing of GO by the intercalation of CNF macromolecules.45,55 In the
ZUO AND YUAN 1883

FIGURE 7 Experimental circuit and fire-warning mechanism diagram

FIGURE 8 Snapshots of fire-alarm testing process of CNF-MMT-GO-30%

XRD pattern of the char residue of CNF-MMT-GO-30%, the charac- The FTIR spectrum of CNF-MMT-GO-30% (Figure 11B) before
teristic peak of GO at 7.81 disappears after combustion and only a combustion shows the characteristic peaks at 3381, 1721, 1425, and
broad peak located at 21.94 is observed, indicating that most 1060 cm−1, corresponding to the vibrations of hydroxyl and carbonyl
oxygen-containing functional groups in GO were removed during the groups and the deformation vibration of C H and C OH, respec-
combustion and then GO was thermally reduced.56 tively.57-60 In the FTIR spectrum of CNF-MMT-GO-30% after
1884 ZUO AND YUAN

FIGURE 9 Snapshots of fire-alarm testing process of CNF-MMT-GO-40%

FIGURE 10 Snapshots of fire-alarm testing process of CNF-MMT-GO-50%

combustion, the characteristic bands of hydroxyl groups, carbonyl oxygen functional groups disappear, confirming the thermal reduction
−1
groups, and C H weaken or disappear. Only the C OH (1101 cm ) of GO after combustion.
peak is still observed. The characteristic peak at 1558 cm−1 is attrib- As shown in Figure 12A, the char residue of CNF-MMT consists
uted to the stretching of graphene, and the bands characteristic of of solid particles, which block the contact between the composite
ZUO AND YUAN 1885

F I G U R E 1 1 A, X-ray diffraction (XRD) patterns of GO and CNF-MMT-GO-30% before and after combustion. B, Fourier transform infrared
(FTIR) spectra of CNF and CNF-MMT-GO-30% before and after combustion

FIGURE 12 Scanning electron microscope (SEM) images of, A, CNF-MMT and B, CNF-MMT-GO-30% after combustion

aerogel and the external oxygen, achieving the flame-retardation 25 C for CNF-MMT-GO-30%, due to the porous structure. The com-
effect. As presented in Figure 12B, the interconnected graphene net- posite aerogel with MMT and GO shows excellent flame-retardant
work is observed after the combustion, and a conductive graphene properties. GO is rapidly reduced to a conductive reduced GO under
path is formed. Thus, the fire-alarm signal is emitted from the lamp the flame, providing a timely alarm signal. The fire-warning mechanism
when the circuit is transformed from the electrically insulating to the of the aerogel is thus explained. This study has demonstrated an inno-
conducting state (Figure 7). vative and multipurpose TIM with flame-retardant and fire-warning
functions, which can effectively solve the shortcomings of traditional
organic TIMs and provide a novel idea for fire-alarm sensors.
4 | C O N CL U S I O N S
AC KNOW LEDG EME NT S
CNF-MMT-GO aerogels were produced by an environmentally The authors wish to express their thanks to Yong Wang, Chengran
friendly vacuum freeze-drying method. The resultant aerogels are Cao, Gongqing Chen, Hongji Tao, and Fangzhou Yang for their assis-
lightweight and pressure-proof, and have excellent thermal insulation tances with the experiments. This work was supported by the
property, exhibiting a low thermal conductivity of 39 mW mK−1 at National Natural Science Foundation of China (51703175) and the
1886 ZUO AND YUAN

National Innovation and Entrepreneurship Training Program for Col- 17. Jiang S, Zhang M, Li M, Liu L, Liu L, Yu J. Cellulose nanofibril (CNF)
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