Composites Part B 220 (2021) 108997

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Thermal-insulating, flame-retardant and mechanically resistant aerogel

based on bio-inspired tubular cellulose
Jiaming Sun a, b, Zhenwei Wu a, b, Bang An a, b, Chunhui Ma a, b, Lifei Xu a, b, Zhanshuo Zhang a, b,
Sha Luo a, b, Wei Li a, b, **, Shouxin Liu a, b, *
a
Key Laboratory of Bio-based Material Science and Technology of the Ministry of Education, Northeast Forestry University, Harbin, 150040, China
b
Engineering Research Center of Advanced Wooden Materials of the Ministry of Education, Northeast Forestry University, Harbin, 150040, China

A R T I C L E I N F O A B S T R A C T

Keywords: Inspired by the tubular structures found in naturally occurring thermal-insulating materials, tubular cellulose
Cellulose aerogel aerogels with improved mechanical resistant, thermal-insulating and flame-retardant properties were prepared
Hollow structure from kapok fibers via a facile process. In contrast to fragileness of traditional organic-inorganic composites, an
Flame retardancy
optimized sample exhibited an ultra-high compressive strength of 32 MPa. The tubular structure of this material
Thermal insulation
resulted in a 37.4 ◦ C increase in heat preservation compared with that obtained from a pulp aerogel without this
N, P doped
morphology. The H3PO4 decomposed from (NH4)2HPO4 in the formulation crosslinked the outermost cellulose
fibers to generate a clay-reinforced dense carbon layer in conjunction with montmorillonite, which restricted the
movement of flames and the outflow of volatile compounds. The gaseous voids of internal tubular fibers inter­
rupted the heat transport pathways to inhibit thermal transmission and trapped combustible volatiles to reduce
the penetration pressure experienced by the dense carbon layer greatly. The combined effects of the carbon layer
and tubular structure effectively limited the transfer of heat, oxygen and volatiles, leading to non-combustion of
the optimal sample. This study provided a cost-effective and facile approach to prepare of thermal-insulating,
fire-safe and high-strength aerogel showing promising applications in exterior wall insulation and vehicle
interior.

1. Introduction hydroxyapatite [11], montmorillonite (MMT) [12], sepiolite [13] and

exfoliated clays [14] into various matrices is commonly used to prepare
Department of Emergency Management Fire and Rescue of China organic-inorganic composites with superior flame-retardant properties.
claimed that there were more than 250 000 fires in 2020 alone, leading Intumescent flame retardants containing N and P are also frequently
to a direct property loss of RMB 2.55 billion. At the same time, the ca­ employed [15,16] because of advantages such as plasticization, low
sualties caused by residential fires are the largest among all fires. costs, limited environmental impact and synergistic effects [17]. Previ­
Improving the fireproof performance of external wall insulation mate­ ous studies have demonstrated that inorganic fillers can also interact
rials will be beneficial to fire prevention and control. Cellulose aerogels with N and P-based additives to produce further synergistic
exhibit high porosity, low thermal conductivity, readily tuned surface flame-retardant effects [18,19]. However, the addition of inorganic
chemistry and minimal density, which have applications as thermal fillers generally reduces the strength of the composite as a result of poor
insulation, energy storage materials, catalyst supports, adsorbents and compatibility with the polymer network that can degrade the physical
electromagnetic shielding [1–10]. However, because the inherent properties of the material [20–22]. Therefore, improvements in the
flammability of cellulose has greatly limited the use of these aerogels, strength of flame-retardant cellulose aerogels are urgently required.
there has been interest in the development of flame-retardant cellulose The structure of a material determines many of its properties, and
aerogels over the past few years. Incorporating inorganic fillers such as tubular morphologies are responsible for many of the specific

* Corresponding author. Key Laboratory of Bio-based Material Science and Technology of the Ministry of Education, Northeast Forestry University, Harbin,
150040, China.
** Corresponding author. Key Laboratory of Bio-based Material Science and Technology of the Ministry of Education, Northeast Forestry University, Harbin,
150040, China.
E-mail addresses: [email protected] (W. Li), [email protected] (S. Liu).

https://doi.org/10.1016/j.compositesb.2021.108997
Received 19 February 2021; Received in revised form 9 May 2021; Accepted 12 May 2021
Available online 18 May 2021
1359-8368/© 2021 Elsevier Ltd. All rights reserved.
J. Sun et al. Composites Part B 220 (2021) 108997

characteristics of various flora and fauna. As an example, the hollow samples according to ASTM D2863-2009, and the dimension of the
hairs of polar bears and mink provide protection from severe cold [23, sample was 100 mm × 10 mm × 10 mm. Thermal conductivity was
24]. The multi-channel internal structures of bird feathers also serve to measured by a thermal analyzer (Hot Disk 2500, Sweden) with transient
greatly reduce the mass of the feathers and provide a thermal barrier plane sources technology at room temperature with a heating power of
[25,26]. Kapok fibers have unique tubular structures together with an 5 mW. Each sample was measured 5 times, and the average value was
exceptionally high hollowness of 97% and are readily available, inex­ used as the result. Thermogravimetric analysis was performed by using a
pensive and lightweight, with low thermal conductivity. Thus, these thermogravimetric analyzer (TG209 F1, Netzsch, Germany) according
materials are often used as insulators in daily life [27–29]. Recently, our to ISO 22007-2 test standard. About 5 mg samples were heated at a
group prepared cellulose aerogels from tubular kapok fibers via an heating rate of 10 ◦ C/min from 25 ◦ C to 800 ◦ C under an air atmosphere.
efficient synthetic process for using as electrode materials, taking Thermogravimetric infrared (TG-IR) of the samples was performed on
advantage of the tubular structures to promote the flow of electrolytes the TGA Q5000 IR thermogravimetric analyzer interfaced to the Nicolet
[30,31]. Furthermore, in view of the lifting effect of tubular structures 6700 FTIR spectrophotometer.
on thermal insulation materials, this type of aerogel could also have
applications as a thermal insulation. However, the majority of tubular 2.3. Preparation of a flame-retardant tubular cellulose aerogel
aerogels are produced using a complicated template method or expen­
sive carbon nanotubes [32–34]. There are two points in the preparation The synthesis route to the aerogel is shown in Fig. 1a. Briefly, 70 mL
process that almost all of aerogels need to be improved. Firstly, the of a kapok fiber cellulose suspension (containing 0.6 g of solids) and 30
formation of sol process is tedious, which cannot avoid solvent recovery mL of an MMT suspension (containing 0.3 g of solids) were transferred
issue and expensive cost [28–30]. Secondly, hardly any of them can into a beaker, after which varying amounts of (NH4)2HPO4 (0, 0.03, 0.06
avoid the use of freeze drying or supercritical CO2 drying, which runs or 0.12 g) were added to the beaker. After stirring for 3 h, each mixture
counter to the popular concept of low energy consumption and facile was filtered through a Buchner funnel to obtain a series of hydrogels
fabrication [31,32]. It would be inchoate and beneficial to instead with the same size. After drying in an oven at 60 ◦ C for 6 h, the flame-
employ natural tubular structures to construct cellulose aerogels for retardant tubular cellulose aerogels (CA-MMT-NPx) were obtained.
thermal insulation applications, in conjunction with simplified fabrica­ Herein, these samples are referred to as CA-MMT-NP0, CA-MMT-NP1,
tion processes. CA-MMT-NP2 and CA-MMT-NP3. A sample was also produced without
The present work developed a tubular cellulose aerogel that displays (NH4)2HPO4 or MMT in the same manner and is referred to herein as the
flame-retardant and thermal-insulating properties together with high CA specimen. In addition, another specimen was synthesized using the
mechanically resistance, by combining kapok fibers with (NH4)2HPO4 same process as used to obtain the CA-MMT-NP3 but employing soft­
and MMT as intumescent flame retardants. Combustion characteristics, wood pulp fibers (which are not tubular) as the raw material. This
the flame-retardant mechanism and the effects of this tubular structure sample is denoted as the pulp fiber aerogel. The actual residual MMT
on thermal insulation properties were investigated. The gaseous voids in content was estimated based on the average of the weight difference
the tubular morphology were found to break the continuity of heat after 5 times of filtration; the actual residual (NH4)2HPO4 content was
transport pathways, which inhibits thermal transmission and to restrict estimated based on the volume of filtrate and the titration data.
the movement of combustible volatile compounds. This lightweight
flame retardant tubular cellulose aerogel offers improved strength and 3. Results and discussion
thermal insulation properties via a facile method, which remarkably
improves flame protection of cellulose aerogel showing practical ap­ 3.1. Synthesis and characterization
plications in exterior wall insulation and vehicle interiors.
In this work, the CA-MMT-NPx specimens were prepared using a
2. Experimental simple blending-filtration-molding process followed by atmospheric
drying (Fig. 1a). In the first step, lignin and waxy substances were
2.1. Materials and characterization removed from the kapok fibers by dealing with NaClO2 and CH3COOH.
The disappeared bands at 1595.25, 1504.09 and 1461.65 cm− 1 in FTIR
Shanghai Aladdin Chemical Reagent Co., China provides CH3COOH, spectrum corresponding to aromatic rings and aliphatic alcohols can
NaClO2, (NH4)2HPO4 and MMT. Raw kapok fibers were from Nanning, verity this discuss (Fig. S1) [35]. The processed kapok fibers were sub­
China. Details regarding the materials used in this work are provided in sequently blended with (NH4)2HPO4 and MMT in a simple procedure.
Supplementary Material. Each mixture was subsequently filtered to generate a wet gel that was
then dried in an oven. As a result of hydrogen bonding and the cross­
2.2. Characterization linking effect of the phosphate ions, the kapok fiber cellulose became
tightly entwined during the suction filtration step.
Scanning electron microscope (SEM) images were acquired on a CA was determined to be composed of a three-dimensional (3D)
Quanta 200 (American FEI Company) operating at an acceleration network of intertwined tubular fibers (Fig. 1c) with diameters of
voltage of 5 kV. The X-ray photoelectron spectroscopy (XPS) was per­ approximately 13 μm and thicknesses of approximately 0.8 μm (inset to
formed on a Thermo scientific Escalab 250Xi. Fourier transform infrared Fig. 1g). In a conventional nanocellulose-based aerogel, the fine fiber
spectroscopy (FTIR) was carried out using an infrared spectrometer network cannot resist the effect of surface tension during the atmo­
(TENSOR 27, Bruker, Germany). The mechanical strength was assessed spheric drying and so the aerogel tends to shrink into a xerogel [33]. In
by using a universal testing machine (Mark-10, USA) with a speed of contrast, the larger kapok fiber cellulose resisted structural shrinkage or
30.0 mm/min at room temperature. The thermographic images were collapse during drying process. After doping with MMT, the surface of
obtained by an infrared thermal camera (FLIR A35). The combustion microtubes is obviously rougher but even (Fig. 1h and i). Under higher
behaviours of the samples were conducted on a cone calorimeter (ISO magnification of SEM images (Fig. 1f and j), the agglomerated MMT
5660, Fire Testing Technology Ltd., Britain) according to the ISO 5560 particles are connected to each other, covering the original texture and
test standard under heat flux of 35 kW m− 2. The vertical burning test grains of fibers. Fig. S2 can further prove that the MMT can be homo­
were performed on a CZF-2-type instrument ( Nanjing Jiangning Anal­ geneously dispersed in matrix. Furthermore, MMT composed of Al2O3,
ysis Instrument Company, China). The limiting oxygen index (LOI) test SiO2 and other hydrophobic substances forms a waterproof protective
using an oxygen index meter (JF-3, Nanjing Jiangning Analytical In­ layer on the surface of the tubular cellulose. As shown in Fig. 1b,
strument, China) were performed to assess the combustion behavior of CA-MMT-NP3 has an average water contact angle of 120.8◦ , which

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J. Sun et al. Composites Part B 220 (2021) 108997

Fig. 1. (a) Diagram showing the preparation of the CA-MMT-NPx specimens. (b) The water contact angle of CA-MMT-NP3. SEM images of (c), (g) the CA; (d), (h) the
CA-MMT-NP0; (e), (i) the CA-MMT-NP3. (f), (j) SEM images comparing the CA and CA-MMT-NP3.

illustrates that CA-MMT-NP3 is hydrophobic. Hydrophobic surface can processing of the fibers, suggesting the formation of hydrogen bonds
address the moisture sensitivity of cellulose aerogel and is conductive to between the CA and (NH4)2HPO4 [36–38]. The appearance of a peak at
dealing with complex environments in practical application. approximately 1446.10 cm− 1 corresponding to C–N stretching estab­
There were no significant differences in the FTIR spectra obtained lished the successful N-doping of the cellulose [39–41]. Compared with
from the CA and CA-MMT-NP0 (Fig. 2a), indicating that only pure the CA, the XPS data obtained from the CA-MMT-NP3 showed significant
physical blending occurred among cellulose and MMT. The peak at increases in the N 1s, Si 2s, P 2p, Si 2p and Al 2p peaks at 401.0, 150.5,
approximately 3384 cm− 1 (attributed to N–H and/or O–H stretching 131.4, 100.1 and 72.9 eV (Fig. 2b), respectively, demonstrating the
vibrations) was shifted to a significantly lower wavenumber after successful introduction of the MMT and (NH4)2HPO4. The deconvoluted

Fig. 2. (a) FTIR spectra obtained from the CA, CA-MMT-NP0 and CA-MMT-NP3. (b) XPS survey spectra for the CA and CA-MMT-NP3. (c) High-resolution C 1s XPS
spectra for the CA and CA-MMT-NP3. (d–e) High-resolution N 1s and P 2p XPS spectra for the CA-MMT-NP3.

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J. Sun et al. Composites Part B 220 (2021) 108997

N 1s and P 2p peaks also confirmed covalent interactions between the

λg0 Π
(NH4)2HPO4 and CA [42]. More detailed analyses of the FTIR and XPS λg = ,
1 + 2βKn
results are provided in the Supplementary Material.
where λg0 = 25 mW m− 1 K− 1 represents the gaseous thermal conduc­
3.2. Thermal insulation performance
tivity in free space, Π is the porosity, β is a constant with a value of
approximately 2 for the air in an aerogel and Kn represents the Knudsen
Comparison tests indicated that the tubular structure had a better
number. This number, in turn, was calculated using the relationship:
thermal insulation effect. As noted, a pulp fiber aerogel was fabricated
from softwood pulp fiber cellulose employing the same method as used lm
Kn = ,
to obtain the CA-MMT-NP3. The pulp fiber aerogel was composed of δ
belt-like fibers (Fig. 3a), while the CA-MMT-NP3 comprised unique
where lm (with a value of approximately 70 nm) represents the mean
tubular fibers (Fig. 3b). Samples of both materials having the same di­
free path of a gas molecule and δ is the pore diameter. The effective solid
mensions were placed on a hot plate heated to 170.3 ◦ C for 10 min, and
conductivity, λ*sol, was determined using the equation:
the difference between the hot plate temperature and the surface tem­
perature (ΔT) of the CA-MMT-NP3 was found to be 37.4 ◦ C greater than λsol
λ*sol = ,
the value obtained with the pulp fiber aerogel. This result indicated that 1 + λsol Rdk
the CA-MMT-NP3 provided a better thermal insulation effect (Fig. 3c and
d, Figure S3). This difference can be attributed to the unique tubular where RK is the Kapitza interfacial thermal resistance and d is the par­
structure of the CA-MMT-NP3, in which the gaseous voids resulted in ticle size.
discontinuous heat transport pathways and so inhibited thermal trans­ Using this approach, λg and λ*sol were determined to be approxi­
mission through the aerogel [32]. mately 2 and 55 mW m− 1 K− 1, respectively, for the CA-MMT-NP3. De­
To further evaluate the thermal insulation performance, a series of tails of these calculations are provided in Discussion 1–2 in the
infrared images were acquired from a CA-MMT-NP3 specimen as the Supplementary Material.
stage was heated from 40 to 170 ◦ C, with representative images pre­
sented in Fig. 3e− h. In these trials, higher ΔT values indicated better 3.3. Flame retardant properties
thermal insulation characteristics, and a ΔT of 113.7 ◦ C was obtained
when the stage was heated to 171.3 ◦ C for 10 min (Fig. 3i). This result Direct flame ignition trials were performed to visually assess the
demonstrated exceptional insulation properties, and the CA-MMT-NP3 combustion characteristics of the various aerogels (Fig. 4a and b). CA
(which had a density of 41 mg cm− 3) was determined to have a thermal was highly flammable and began to burn immediately after coming into
conductivity of 0.054 W m− 1 K− 1. Fig. 3j provides a diagram summa­ contact with an ignition source, followed by rapid flame propagation
rizing the factors associated with the thermal conductivity through the (Fig. 4a and Video S1). The flame was extinguished while burning
tubular structure of this material, based on convection, radiation as well violently over a span of 30 s and exhibited smoldering for a long time. In
as conduction through gases and solids [13]. According to other studies contrast, the CA-MMT-NP0 burned and smoldered slowly for 120 s and
[13,43], the convection and radiation contributions could be ignored at left a loose, dark grey residue (Fig. 4b). Those samples containing
ambient temperature because of the small pore sizes in the fiber walls (NH4)2HPO4 showed self-extinguishing behavior. The CA-MMT-NP1
and the comparatively low temperature. The heat conduction through produced only a faint flame and exhibited slower spreading of the fire.
the gas phase (λg) was highly correlated with the degree of porosity in The flame was observed to die out after burning for 8 s and no smol­
the aerogel and was calculated as: dering occurred (Video S2). The burning time of the aerogels decreased
with increasing of the (NH4)2HPO4 content because of the gradually

Fig. 3. SEM images of the (a) pulp fiber aerogel and (b) CA-MMT-NP3. Side view pseudo-color thermal image of the (c) pulp fiber aerogel and (d) CA-MMT-NP3 with
a height of 1 cm after heating for 10 min. Top side pseudo-color thermal images of the CA-MMT-NP3 with a height of 1 cm after heating for 1, 5 and 10 min on a hot
plate held at (e) 60, (f) 80, (g) 100 and (h) 170 ◦ C. (i) The temperature differences (ΔT) between the surface of the hot stage and the CA-MMT-NP3 surface as
functions of temperature. (j) A diagram summarizing the factors contributing to thermal conductivity in the tubular CA-MMT-NP3 structure. (For interpretation of the
references to color in this figure legend, the reader is referred to the Web version of this article.)

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J. Sun et al. Composites Part B 220 (2021) 108997

Fig. 4. (a) Photographic images of the combustion of the CA over time. (b) Photographic images of different CA-MMT-NPx after combustion (The labels located at
lower right corner of photos are total burning time); (c) TG, (d) DTG, (e) HRR, (f) THR, (g) CO2 production and (h) CO production data for various specimens.

strengthened self-extinguishing effect (Fig. 4b), such that the CA-MMT- CA-MMT-NP0, suggesting that the addition of (NH4)2HPO4 resulted in an
NP3 was difficult to even ignite (Video S3) and showed oxidation rather early onset of degradation. The (NH4)2HPO4 would have generated
than combustion with a flame. This process consumed oxygen in H3PO4 during the decomposition process, and this compound would
conjunction with a very low heat release rate, and could be monitored have catalyzed the dehydration of the cellulose and promoted char
using cone calorimetry. LOI and vertical burning tests were further used formation at elevated temperatures. Simultaneously, the connected
to evaluate the combustion behavior of CA and CA-MMT-NP3. As shown MMT nanoplatelets likely formed a barrier that insulated the fibers and
in Table 2, LOI value of CA was 17.8%. During the vertical burning test, protected them from O2. The analysis of single components proves cat­
CA produced a large flame until burning out, and failed to pass vertical alytic carbonization ability from another aspect. According to the TG
burning test. In contrast, CA-MMT-NP3 with a high LOI value of 43.9% results of single components in Fig. S4, the char yields of cellulose, MMT
only exhibited smoldering during the whole vertical combustion tests. and (NH4)2HPO4 are 0.91%, 82.84% and 15.17%, respectively.
No flame can be observed after the removal of flame. CA-MMT-NP0 is composed of cellulose (85.71%) and MMT (14.29%).
Supplementary data related to this article can be found at https://do CA-MMT-NP3 is composed of cellulose (83%), MMT (13.8%) and
i.org/10.1016/j.compositesb.2021.108997. (NH4)2HPO4 (3.2%). According to the actual char yield in Table 1 and
On the basis of these ignition tests, the CA-MMT-NP3 was further the theoretical data that calculated by liner combinations of the exper­
assessed using TG in air. The CA showed a two-step thermal decompo­ imental TG curves of single components in Fig. S4, the actual char yield
sition process under air, related to the formation of aliphatic char and (28.47%) of CA-MMT-CA0 is greater than the theoretical calculation
flammable volatiles over the range of 200–324 ◦ C and the oxidation of yield (12.62%), which proves that MMT does have a protective effect on
the aliphatic char to aromatic char with the release of CO and CO2 above the cellulose during the combustion process. This protective effect is also
325 ◦ C (Fig. 4c) [44–46]. CA is composed of pure cellulose, which is easy proved by the phenomenon in Fig. 5a~d. Furthermore, the actual char
to degradation. Therefore, the weight of CA decreases dramatically yield (46.86%) of CA-MMT-CA3 is greater than the theoretical calcula­
when heated in air atmosphere. The addition of MMT did not change this tion yield (12.68%) of CA-MMT-CA3 or the actual char yield (28.47%) of
two-step thermal oxidation but led to a higher thermal-oxidative sta­ CA-MMT-CA0, which indicates that (NH4)2HPO4 further promotes the
bility and residue. A greater amount of residue was also obtained from formation of the char. The catalytic char-forming effect of the
samples incorporating the (NH4)2HPO4. The decomposition onset tem­ (NH4)2HPO4 and the barrier properties of the MMT both worked to
perature (Tonset) was defined as the temperature corresponding to a mass improve the thermal stability of the CA-MMT-NP3 and to produce more
loss of 5%, while the temperature at which the maximum degradation residue.
rate appeared was termed Tmax [17]. The data in Table 1 indicate that The cone calorimeter data in Table 2 established that the time from
the Tonset value of the CA-MMT-NP3 was lower than that of the ignition to flameout (ITF) was greatly affected by the presence of
(NH4)2HPO4. Specifically, the ITF value for the CA-MMT-NP3 was 37s
Table 1 longer than that of CA. This change can be attributed to the isolating
Thermal degradation data for the CA, CA-MMT-NP0 and CA-MMT-NP3. effect of the carbon layer, which limited the supply of oxygen to the
fibers.
Sample Tonset (oC) Tmax(oC) Residue (wt%)
When exposed to a 35 kW m− 2 heat flux, the CA burned rapidly to
CA 64.89 281.56 0.91 generate a high peak heat release rate (PHRR) and a high total heat
CA-MMT-NP0 263.52 318.92 26.13
release (THR) (Table 2). After adding the MMT, two HRR peaks
CA-MMT-NP3 192.86 314.06 46.86

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J. Sun et al. Composites Part B 220 (2021) 108997

Table 2
Cone calorimeter data for the CA and CA-MMT-NPx.
Sample TTI (s) ITF (s) PHRR (kW m− 2) FPI (s m2 kW− 1) FGI (kW m− 2 − 1
s ) THR (MJ m− 2)
TSR (m2 m− 2) LOI (%)

CA 4 48 199.13 0.020 6.64 10.87 5.12 17.8

CA-MMT-NP0 5 52 164.49 0.030 5.48 12.91 3.40 26.2
CA-MMT-NP1 6 63 158.48 0.038 3.17 11.25 2.34 31.3
CA-MMT-NP2 6 80 82.63 0.073 1.18 8.65 1.75 39.8
CA-MMT-NP3 9 85 53.11 0.17 0.70 5.51 1.27 43.9

appeared during the combustion process (Fig. 4e). The first peak performance should have high FPI and low FGI [49]. CA has the high­
occurred at 20 s with a PHRR of 164 kW m− 2 and originated from surface est FGI and the lowest FPI. With the addition of (NH4)2HPO4, the FPI
combustion, which was hampered by the physical surface barrier value increases and the FGI decreases, indicating that the presence of
generated by the MMT. The second peak appeared at 45 s with a PHRR (NH4)2HPO4 can reduce the fire hazard. The CA-MMT-NP3 has a higher
of 155 kW m− 2 and was ascribed to the internal combustion of the FPI and a lower FGI, which demonstrates that it has the best flame
specimen. The incorporation of MMT resulted in a 17.59% reduction in retardancy. The average effective heat combustion (av-EHC) value in­
the PHRR value, although the THR of the CA-MMT-NP0 was lower than dicates the extent to which volatile compounds in the gas phase are
that of the CA over the first 62 s, after which it became higher (Fig. 4f). burned during combustion, with a low av-EHC reflecting a higher pro­
This time span corresponded to the time at which the flame on the CA- portion of nonflammable gases [17]. The av-EHC for the CA-MMT-NP3
MMT-NP3 sample was extinguished. And this effect can be attributed to of 0.65 MJ kg− 1 was significantly lower than that of 3.68 MJ kg− 1 for the
the barrier effect of the MMT, which suppressed the migration of heat CA. This difference is attributed to the release of nonflammable gases
such that the heat release occurred more slowly during combustion. The such as phosphide and NH3 from the CA-MMT-NP3 during the com­
reduced heat release rate would be expected to reduce fire hazards. bustion process, as confirmed by thermogravimetric infrared (TG-IR)
These results showed that MMT was able to reduce the burning rate of spectroscopy [50]. These volatile compounds serves to dilute the flam­
the fibers, but could not completely prevent combustion. However, mable gases and oxygen around the fuel, therefore hindering the prop­
incorporating the (NH4)2HPO4 drastically reduced both the PHRR and agation of flames and reducing the fire risk.
THR values (Fig. 4e− f), such that the PHRR/THR values for the CA-
MMT-NP1, CA-MMT-NP2 and CA-MMT-NP3 were decreased by 20.41%/
14.81%, 58.50%/20.42% and 73.33%/49.31%, respectively, relative to 3.4. Analysis of char residue and possible flame-retardant mechanism
those for the CA. In addition, as the (NH4)2HPO4 content was increased,
the first HRR peak generated by members of the CA-MMT-NPx series Assessing the flame-retardant mechanism associated with these
appeared earlier, as a consequence of the catalytic decomposition of this materials required a structural analysis of the residual char. Compared
additive (Fig. 4e). Evidently, the (NH4)2HPO4 decomposed and then with the CA, which completely combusted leaving no residue (Fig. S5), a
stimulated the degradation and carbonization of the cellulose matrix small amount of grey residue was left after combustion of the CA-MMT-
during combustion. The dense protective layer resulting from these NP0 (Fig. 5a). The original shape of the sample could still be discerned
processes isolated the condensed phase, such that the CA-MMT-NP3 had after burning (Fig. 5b− d). These results indicated that the addition of
the lowest PHRR and THR. These data further confirmed the superior MMT helped to preserve the cell walls during combustion.
flame retardant properties of the CA-MMT-NP3 that resulted from its The CA-MMT-NP1 produced a black, fragmented residue (Fig. 5e). In
heat release characteristics. contrast, the CA-MMT-NP3 produced a complete, coherent and dense
In an actual fire, smoke and toxic gases such as CO2 and CO can char layer (Fig. 5m). The increases in the proportion of (NH4)2HPO4
produce a risk of suffocation and so the evolution of such gases should increased the amount of char (Fig. 5e, i and m), demonstrating that this
also be considered. According to Table 2, the total smoke release (TSR) additive promoted char formation. The (NH4)2HPO4 also appeared to
values for the CA-MMT-NP1, CA-MMT-NP2 and CA-MMT-NP3 were promote crosslinking of the cellulose. The CA-MMT-NP0 showed no
reduced by 68.55%, 72.46% and 75.19%, respectively. These remark­ evidence of crosslinking between the remnants of the tubular fibers
able reductions indicated that the stable char layer formed on these (Fig. 5b), while the surface of the residual char exhibited crosslinking
materials reduced the fuel supply and thus inhibited the production and and the formation of a barrier after adding the (NH4)2HPO4 (Fig. 5f, j
release of CO, CO2, water and particulate matter generated during and n). It is worth noting that the resulting carbon layer gradually
combustion [47]. The complete combustion of cellulose produces CO2, became stronger as the (NH4)2HPO4 content was increased. This was
while the formation of CO is attributed to incomplete combustion caused demonstrated by the swollen coatings that could be clearly seen on the
by smoldering [48]. The data in Fig. 4g and h demonstrate that, in CA-MMT-NP2 and CA-MMT-NP3 samples after combustion, appearing as
general, CO peaks appeared after CO2 peaks in all samples, because bubbles (Fig. 5 j and n). The majority of the bubbles on the CA-MMT-NP2
smoldering occurred after the flames were extinguished. The CA was were damaged and cracked (see the red circles in Fig. 5j), whereas they
completely combusted because no char layer was produced to act as a appeared nearly intact and undamaged on the CA-MMT-NP3 (blue cir­
barrier, and so the CO2 production (CO2P) value for the CA was cles in Fig. 5n).
accompanied by a minimal CO production (COP) value (Fig. 4g and h). The phosphate served to crosslink the outermost cellulose fibers that
With the addition of MMT and (NH4)2HPO4, a char layer was generated were in direct contact with the flame, to form a char layer, and also
that had a barrier effect, leading to an insufficient oxygen supply. The strengthened the barrier effect of individual fibers inside. As shown in
resulting suppression of complete combustion greatly increased the CO Fig. 5c and d, each fiber of the CA-MMT-NP0 became severely shrunk or
output. Furthermore, as the (NH4)2HPO4 content was increased, the even transparent after combustion. However, after the (NH4)2HPO4 was
ongoing formation of this char layer further reduced the migration of added, the tubular structure was preserved, instead leaving many small
combustible gases, such that there was a continual decrease in the TSR holes on the tubes (red circles in Fig. 5h). As the (NH4)2HPO4 content
values (Table 2). was increased, the ability of the carbon layer to restrict the movement of
To determine the fire hazard clearly, the fire performance index (FPI) volatiles increased. The small holes also gradually transitioned to
and fire growth index (FGI) are shown in Table 2. The FPI is assigned to coexistence of broken and complete bubbles (Fig. 5l) and eventually
the ratios of TTI to PHRR values. The FGI is defined as the ratio of PHRR only complete bubbles were obtained (Fig. 5p). Thus, the tubular
values and the time to PHRR. The composites with high fire-resistant structure effectively suppressed the leakage of volatiles from the
microtubes and greatly reduced the osmotic pressure at the outermost

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J. Sun et al. Composites Part B 220 (2021) 108997

Fig. 5. Photographic images of char residues after cone tests for the (a) CA-MMT-NP0, (e) CA-MMT-NP1, (i) CA-MMT-NP2 and (m) CA-MMT-NP3. SEM images of
these same chars for the (b)–(d) CA-MMT-NP0, (f)–(h) CA-MMT-NP1, (j)–(l) CA-MMT-NP2 and (n)–(p) CA-MMT-NP3.

char layer. CO2 (2380 and 2300 cm− 1), CO (2248 cm− 1), compounds containing
The absorbance value for the CO2 peak appearing in the 3D FT-IR carbonyl groups (1760 cm− 1) and ethers (1174 cm− 1) [51,52]. The
spectra was reduced from 0.16 to 0.06 as the MMT and (NH4)2HPO4 pyrolysis products of the CA-MMT-NP3 were similar, but some differ­
were added (Fig. 6a and b), which was ascribed to the strong barrier ences could be observed. Specifically, a new absorption band appeared
effect obtained from the MMT and the charring effect of the at 1510 cm− 1 corresponding to aromatic rings [15] along with peaks
(NH4)2HPO4. Fig. 6c and d provide the corresponding FT-IR spectra between 910 and 1050 cm− 1 that were attributed to the release of NH3
acquired at different temperatures. These data indicate that the major from the (NH4)2HPO4 [53]. This process would dilute the flammable
gaseous products generated by the CA were water (3600− 3800 cm− 1), gases and oxygen around the matrix, therefore hindering the

Fig. 6. The 3D TG-FTIR spectra and corresponding FTIR spectra at different temperatures under a N2 atmosphere obtained from the (a, c) CA and (b, d) CA-MMT-NP3
after pyrolysis. (e) FT-IR and (f) Raman spectra of the residual chars.

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J. Sun et al. Composites Part B 220 (2021) 108997

propagation of the fire. The decomposed H3PO4 also promoted dehy­ flammable gases and oxygen around the matrix, thus hindering the
dration of the cellulose to produce char, as indicated by the constant propagation of the fire.
generation of H2O at high temperatures in Fig. 6d. Structurally, when the CA-MMT-NP3 is exposed to the flame, the
Because the CA was completely combusted during the cone calo­ catalytic char-forming ability of H3PO4 crosslinks the outermost cellu­
rimeter tests, the CA-MMT-NP0 was instead used as a blank control lose fibers (those in direct contact with the flame) to form a clay-
sample in the FTIR and Raman analyses. The peaks at 1413 and 998 reinforced dense carbon layer, with additional protection provided by
cm− 1 were ascribed to the in-plane bending vibrations of C–H and the MMT. This dense external layer becomes Barrier 1 on the CA-MMT-
Si–O–Si bonds in the residue of CA-MMT-NP0 [12]. (Fig. 6e). Compared NP3 (Fig. 7a− c). In the interior of the aerogel that does not contact the
with CA-MMT-NP0, new peaks located at 3419, 1620 and 1068 cm− 1 are flame, the intact tubular structure becomes Barrier 2 (Fig. 7a and d).
assigned to N/O–H stretching vibrations [17], conjugated aromatic Barrier 1 significantly retards the pervasion of the flame, the supply of
C–– C groups [53] and the overlapping vibrations of P–O–C and P–O–P oxygen and the outflow of volatile compounds (Fig. 7c). This barrier is
bonds [54], respectively. These results demonstrated that some phos­ brittle and fragile when the concentration of (NH4)2HPO4 is very low
phoric was generated from the decomposed (NH4)2HPO4 during com­ and so its protective effect is limited (Fig. 7b). However, at higher
bustion and acted as a dehydration agent to accelerate the formation of concentrations, the resulting barrier is stronger and does not crack upon
char. The Raman spectra showed two bands at approximately 1350 and exposure to a flame or heat flux (Fig. 7c). The hollow structure of Barrier
1580 cm− 1 (the D and G bands), which were ascribed to disordered and 2 breaks the continuity of heat transport pathways and thus decreases
graphitic char, respectively [12,54] (Fig. 6f). The ID/IG value for the thermal transmission by inhibiting convection, reducing conduction and
CA-MMT-NP3 (0.93) was slightly higher than that for the CA-MMT-NP0 multiple reflect radiation. Moreover, Barrier 2 provides a complete and
(0.92), indicating a reduction in graphitic char. This was ascribed to the strong wall that seals in combustible volatiles and suppresses leakage
generation of an amorphous glassy char with catalysis by the from the microtubes (Fig. 7d). These two roles of Barrier 2 greatly
(NH4)2HPO4, which covered the residue and created an impassable layer reduce the penetration pressure experienced by Barrier 1. The two
that resulted in reduced smoke. barriers of CA-MMT-NP3 effectively inhibit the transmission of volatile
Based on the above analyses of the residual char, a flame retardant compounds, heat and oxygen, making CA-MMT-NP3 exhibit flame
mechanism can be proposed. In this mechanism, upon exposure to retardant properties together with self-extinguishing behavior in the
flame, the CA rapidly decomposes until completely burned, accompa­ flammability tests.
nied by the release of large amounts of CO2. This process is related to
heterolytic bond scission along the molecular chains of the cellulose and
results in the generation of levoglucosan, a highly unstable volatile 3.5. Mechanical properties
monomer, which plays a crucial role in cellulose depolymerization [55].
Phosphate attaches to the cellulose and inhibits the production of lev­ The aerogels had low densities, such that samples could be placed on
oglucosan, thereby preventing the depolymerization of cellulose during the petals of a chrysanthemum without any obvious deformation
the burning process [55]. The (NH4)2HPO4 decomposes into NH3 and (Fig. 8a− c). Specifically, the densities of the CA, CA-MMT-NP0 and CA-
H3PO4 and the latter catalyzes the dehydration of cellulose at elevated MMT-NP3 were calculated to be 25.46, 30.54 and 41.53 mg cm− 3,
temperatures, favoring the formation of thermally stable char structures. respectively. In contrast to common aerogels, the CA-MMT-NP3 was also
The water produced during the dehydration of the cellulose and the NH3 found to possess high mechanical resistance together with a low density.
generated by the decomposition of the (NH4)2HPO4 dilute the A 0.6 g sample of the CA-MMT-NP3 could withstand 2500 times its own
mass without deformation, suggesting superior mechanical robustness

Fig. 7. Diagrams showing the flame retardant mechanism. a. The two barriers that were formed, b. Barrier 1, with insufficient (NH4)2HPO4, c. Barrier 1 with
sufficient (NH4)2HPO4 and d. Barrier 2.

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J. Sun et al. Composites Part B 220 (2021) 108997

Fig. 8. Photographic images of the (a) CA, (b) CA-MMT-NP0 and (c) CA-MMT-NP3. (d) Images of a CA-MMT-NP3 specimen withstanding a load of 1.5 kg without any
deformation. (e) Compressive stress-strain curves for various specimens.

(Fig. 8d). After addition of the MMT, the compressive strength of the CA- combustible volatile compounds. A dense, clay-reinforced carbon layer
MMT-NP0 was increased from 860 kPa for the CA to 1.031 MPa under limited the penetration of flames and oxygen into the aerogel while
the strain of 85% (Fig. 8e). The incorporation of the (NH4)2HPO4 greatly restricting the outflow of volatiles. The catalytic carbonization
dramatically reinforced the foam structure, improving the strength to effect of phosphate, the barrier effect provided by the MMT as well as the
32 MPa, which is exceptionally high among reported robust aerogel presence of two structural barriers prevented the direct ignition of the
(Table S1). This significant improvement in compressive strength while optimized sample. This specimen had PHRR and THR values of 53.11
maintaining a relatively low density can be explained by three effects. kW m− 2 and 5.51 MJ m− 2, respectively, corresponding to decreases of
First, density is known to be associated with the strength of an aerogel 73.33% and 49.31% relative to the pristine aerogel. This aerogel is ex­
[16]. In the present case, MMT enhanced the strength of the material by pected to provide significantly improved protection from flames and
increasing its density. Second, the introduction of N and P would be could have applications as an exterior wall insulation, firefighting ma­
expected to form hydrogen and covalent bonds with hydroxyl groups on terials and vehicle interiors.
the cellulose fibers, leading to a more condensed network in the aerogel
and increasing the strength of the material. Thirdly, although the Author contributions
network is strengthened, the tubular structure reduces its density
effectively. Jiaming Sun: Conceptualization, Methodology, Software, Investiga­
tion, Visualization, Writing Original Draft.
4. Conclusion Zhenwei Wu: Editing, Software, Investigation, Visualization.
Bang An: Validation.
This study demonstrated a cost-effective and facile process for the Chuihui Ma: Validation, Formal analysis.
fabrication of flame-retardant tubular cellulose aerogels with improved Lifei Xu: Validation
strength and thermal-insulating characteristics based on the natural Sha Luo: Validation, Formal analysis.
tubular structure of kapok fibers. An optimized sample was found to Zhanshuo Zhang: Validation, Software.
have a unique tubular structure with diameters of approximately 13 μm, Wei Li: Resources, Review & Editing, Supervision.
a low density of 41 mg cm− 3 and an ultra-high compressive strength of Shouxin Liu: Resources, Review & Editing, Supervision.
32 MPa. The gaseous voids in this unique tubular structure disrupt the
transmission of heat-transport pathways leading to a low thermal con­
Declaration of competing interest
ductivity of 0.054 W m− 1K− 1 and a 37.4 ◦ C increase in heat preservation
compared with a pulp aerogel without a tubular structure. The hollow
The authors declare that they have no known competing financial
fibers inhibited heat transmission and also effectively trapped
interests or personal relationships that could have appeared to influence

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J. Sun et al. Composites Part B 220 (2021) 108997

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