Journal Pre-proof

Robust, sustainable cellulose composite aerogels with outstanding flame

retardancy and thermal insulation

Xiaolei Luo, Junyan Shen, Yanan Ma, Lin Liu, Ranju Meng, Juming
Yao

PII: S0144-8617(19)31291-3
DOI: https://doi.org/10.1016/j.carbpol.2019.115623
Reference: CARP 115623

To appear in: Carbohydrate Polymers

Received Date: 11 July 2019

Revised Date: 11 November 2019
Accepted Date: 12 November 2019

Please cite this article as: Luo X, Shen J, Ma Y, Liu L, Meng R, Yao J, Robust, sustainable
cellulose composite aerogels with outstanding flame retardancy and thermal insulation,
Carbohydrate Polymers (2019), doi: https://doi.org/10.1016/j.carbpol.2019.115623

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Robust, sustainable cellulose composite aerogels with outstanding flame

retardancy and thermal insulation

Xiaolei Luoa, Junyan Shena, Yanan Maa, Lin Liua,b,∗ , Ranju Menga, and Juming Yaoa,b,*

a
The Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Edu-

cation, College of Materials and Textiles, Zhejiang Sci-Tech University, 928 Second Avenue, Xiasha

Higher Education Park, Hangzhou 310018, China

b
National Engineering Lab of Textile Fiber Materials & Processing Technology, Hangzhou 310018,

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China

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*Corresponding author
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Pro. Lin Liu

Email address: linliu@zstu.edu.cn (L. Liu)

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Tel.: +86-571-86843618; fax: +86-571-86843619.

Pro Juming Yao

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Email address: yaoj@zstu.edu.cn (J-M. Yao)

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Highlights

 Cellulose aerogels were prepared by incorporating LDH as green nanofiller.

 A novel strategy to exfoliate LDH into nanosheets.

 The cellulose aerogels exhibited dramatically increased mechanical properties.

 Outstanding flame retardancy and smoke suppression performance were achieved

 Enhancement mechanisms of mechanical and flame retardant were well investigated.

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ABSTRACT

Robust and sustainable cellulose composite aerogels were prepared by incorporating MgAl-layered dou-

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ble hydroxide (MgAl-LDH1) as green nanofillers and flame retardants. Two series of aerogels combining
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MgAl-CO3 LDH (MA-C) and MgAl-H2PO4 LDH (MA-P) were achieved, in which both MA-C and MA-

P were uniformly dispersed in cellulose substances. The cellulose composite aerogels with 1.8 wt% of
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MA-C (denoted as CAC) and MA-P (denoted as CAP) displayed excellent mechanical properties, in-

creased by 2.6 and 2.8 times compared with neat cellulose aerogels (CA), respectively. The peak of heat
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release rate (PHRR) of CAC and CAP reduced by 41 % and 50 % compared with the neat one, respectively,
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Acronyms and Abbreviations

LDH: layered double hydroxide; MgAl-LDH: layered double hydroxide prepared with Mg2+ and
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Al3+; MA-C: MgAl-LDH with intercalated anion of CO32-; MA-P: MgAl-LDH with intercalated anion of
H2PO4-; CA: neat cellulose aerogels; CAC: cellulose composite aerogels combining with MA-C; CAP:
cellulose composite aerogels combining with MA-P; MBA: N,N-methylenebisacrylamide; MgAl-LDO:
oxidation of MgAl-LDH under calcination; HRR: heat release rate; PHRR: peak value of HRR cruve;
THR: total heat release; PTHR: peak value of THR cruve; EHC: effective heat of combustion; PEHC:
peak value of EHC cruve; SPR: smoke production ratio; PSPR: peak value of SPR cruve; MLR: mass
loss rate; FPI: fire performance index; FGI: fire growth index.

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demonstrating the outstanding flame retardancy. The reduction in smoke production ratio (SPR) was 79

% for CAC and 75 % for CAP, respectively, indicating enhanced smoke suppression performance. There-

fore, the high performance flame-retardant cellulose composite aerogels exhibit an application prospect

in green advanced engineering field.

Keywords

Cellulose aerogel, Layered double hydroxide, Flame retardancy, Smoke suppression.

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Introduction

Recently, advanced biopolymer materials derived from renewable resources have been considered

as promising candidates to replace traditional petro-polymers as the continuous energy and environmental

concerns (Imre, Garcia, Puglia, & Vilaplana, 2019). In this regard, cellulose aerogel has been the front-

runner in these biopolymer materials due to its high porosity, large specific surface area, low density, high

insulation, low thermal conductivity, sustainability, biocompatibility, biodegradability and low cost. Con-

sequently, cellulose aerogel has great potential applications in aerospace, lightweight building materials,

transportation interiors, packaging materials, insulation materials, flexible devices, effluent treatment, etc

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(Chen et al., 2018; Ye et al., 2018; Wang, Lu, & Zhang, 2016; Fernades, Pires, Mano, & Reis, 2013;

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Ramage et al., 2017; Ren et al., 2018). However, due to its intrinsic inflammability, cellulose aerogel is

easy to ignite almost without residual char formation. Additionally, cellulose aerogel exhibits weak me-

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chanical properties. These hinder its wider application in numerous important fields like lightweight en-

gineering materials and domestic devices. Therefore, enhancement in the mechanical strength and the
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flame retardancy of cellulose aerogel meanwhile maintaining its unique features is a challenge of interest.
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Organic/inorganic nanocomposites have emerged in the field of flame retardancy during last decades

because of their obvious improvements in mechanical properties and flame retardance. Much efforts have

focused on the incorporation of layered clays in polymers, in which clays exerted amazing effects on fire
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properties of polymers (Kiliaris & Papaspyrides, 2010; Wang et al., 2017; Fu et al., 2017). Similar to clay,

layered double hydroxides (LDHs), another kind of two-dimensional layered material, are used as nano-
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fillers for improving the flammability of polymers due to their excellent flame retarded efficiency, smoke
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suppression, sustainability, as well as unique layered structure and tunable chemical composition (Yu,

Wang, O’Hare, & Sun, 2017; Liu, Gao, Wang, & Lin, 2018). Wang et al. introduced 15 wt% Zn2Al-borate

LDH in polypropylene, and found that PHRR was reduced by 63.7 % compare to nanocomposites without

LDH (Wang et al., 2013). Li et al. synthesized an organically modified MgAl-LDH (SIEPDP-LDH) used

as flame retardant for bisphenol epoxy resins, and found that the UL-94 classification of SIEPDP-

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LDH/epoxy with 8 wt% loading passed V-0 (Li, Wan, Kalali, Fan, & Wang, 2015). However, high addi-

tion amount of LDH usually resulted in poor mechanical properties of polymer nanocomposites. To solve

this problem, the synergistic effect of LDH with other flame retardants such as graphene, phosphorus-

containing compounds, and so on, is explored to reduce the addition amount and acquire good flame-

retardant performance. For example, Xu et al. evaluated the effect of graphene/MgAl-LDH modified by

CuMoO4 (RGO-LDH/CuMoO4) on the smoke suppression and flame retardancy of epoxy resin (EP) (Xu,

Zhang, Wang, Wang, & Ding, 2018). Compared with EP, the PHRR and total heat release (THR) of EP

with 2 wt % RGO-LDH/CuMoO4 were decreased by 47.6 % and 28.5 %, respectively. In fact, cellulose

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aerogels have an intrinsic inflammability and relatively weak mechanical strength, which are expected to

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be improved by incorporating LDH. To the best our knowledge, there are little reports on the flame-re-

tardant performance and flame-retardant mechanism of phosphorus intercalated LDH for cellulose aero-

gel.

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In this work, MgAl-CO3 LDH (MA-C) was firstly synthesized using chemical precipitation method.
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H2PO4- was chosen to intercalate into MgAl-LDH (MA-P) by calcination-reconstruction and used as syn-
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ergistic agent for cellulose aerogels to improve flame retardancy and mechanical properties. For excellent

dispersion and interface bonding of LDH in cellulose substance, cosolvent exfoliation of LDH was de-

veloped through NaOH/urea solution which is well known to dissolve cellulose at low temperature. Fi-
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nally, the microstructure, mechanical properties, thermal stabilities, heat insulation, combustible behav-

iors and smoke suppression of cellulose/LDH composite aerogels were systematically investigated. Fur-
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ther, the flame retardant mechanism of the cellulose/LDH composite aerogels was assumed. In a word,
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the concept presented in this work is to develop a robust and sustainable cellulose composite aerogel with

improved mechanical property and flame retardancy by incorporating LDH, a green nanofiller and flame

retardant. This work not only proposes a new insight into preparing high performance cellulose aerogels,

but also provides a novel strategy to exfoliate and disperse LDH nanosheets.

2. Experimental

2.1 Materials
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 Cotton waste was provided by Zhejiang Tiandi Cotton Co., Ltd. NaOH, urea, Na2CO3, AlCl3·9H2O

Mg(NO3)2·6H2O, KH2PO4 were purchased form Shanghai Aladdin Reagents Co., Ltd (China). N,N-meth-

ylenebisacrylamide (MBA) was obtained from Macklin Biochemical Technology Co., Ltd (Shanghai,

China). All chemical reagents are analytical grade and used without further purification.

2.2 Synthesis of LDH

The MgAl-CO3 LDH (MA-C) was first synthesized by co-precipitation method with Mg/Al molar

ratio of 2.0, wherein the concentration of Al3+ is 0.167 mol/L. The pH of the reaction system was adjusted

to pH=10~11 using 0.5 mol/L NaOH solution. The resulting slurry was sealed in an oven at 60 °C for 18

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h. Then, the products (MA-C) were obtained after filtration, washing and freeze drying. Part of MA-C

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was calcined at 550 °C for 5 h, forming MgAl-oxide (MgAl-LDO). Then 1.43 g of MgAl-LDO was mixed

with 0.048 mg/mL KH2PO4 solution (30 mL), and aged at 50 ℃ for 5 h. Finally, the MgAl-H2PO4 LDH

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(MA-P) was harvested by being centrifuged, washed and dried. For conveniently, the MA-C and MA-P

were both called LDH.

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2.3 Preparation of cellulose/LDH composite aerogels
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Firstly, LDH and smashed cotton fiber was dispersed into the precooled 7 wt% NaOH/12 wt% urea

solution (-20 ℃) with a magnetic stirring for 3 min. After that, the mixture was transferred to a refrigerator

at -20 ℃ for 2 h, then dissolved with a mechanically stirring for 10 min at room temperature. Wherein,
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the NaOH/urea solution system not only can dissolve cellulose, but also simultaneously exfoliate the LDH

to form colloidal nanosheets through destroying the original hydrogen-bond network between the adjacent
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LDH layers, similar with cellulose dissolution process at low temperature (Yu, Wang, O’Hare, & Sun,
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2017; Wei, Li, & Liu, 2014). Subsequently, MBA as cross-linker was added into above mixed solution.

After 12 h, the cellulose/LDH composite hydrogels were formed, then washed and freeze-dried. The com-

posite aerogels with different amounts of MA-C or MA-P were denoted as CAC-n or CAP-n to distinguish

with the pure cellulose aerogels (CA), where, n=1, 2,3 representing the amount of MA-C or MA-P of 0.6

wt%, 1.2 wt%, 1.8 wt%, correspondingly. The compositions of all the composite aerogels are listed in

Table S1.
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2.4 Characterization

Morphologies and crystal phases of LDH were determined by Transmission electron microscopy

(TEM, JEM-2100, JEOL, Japan), Field emission scanning electron microscopy (FESEM, JSM-5610,

JEOL, Japan) and X-ray diffractometer (XRD, Bruker D8, Germany). Microstructures of the aerogels

were investigated using a FESEM. Porosity of the aerogels was determined by mercury porosimeter (Au-

toPore IV 9500, Micromeritics, USA). Density of aerogels was calculated according to the ratio of its

mass to volume. Chemical structure of the samples was analyzed by Fourier Transform Infrared Spec-

trometer (FTIR, Nicolet IS50, USA). Thermal stability of the samples was measured by thermos gravi-

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metric analyzer (Netzsch, TG 209 F1, Germany) with a heating rate of 20 °C/min under air flow at 30

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mL/min. Compression performances of the aerogels with diameter of 12.9 mm and height of 13.5 mm

were tested on Instron 5943 universal testing machine (USA). Five replicates were tested for each sample

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with compressing speed of 5 mm/min until deformation of 80 % was achieved at 25 °C. Thermal physical

properties of the aerogels were tested by thermal conductivity meter (Fox 314, TA insuments, US) using
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standard named ASTM C518. Limiting oxygen index (LOI) of the aerogels was determined using an
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oxygen index meter according to the GB/T 5454 (Qingdao Shanfang Instrument, ZR-01, China). Com-

bustion testing was carried out using a cone calorimeter (FTT 003, Fire Testing Technology, US) accord-
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ing to ISO 5660 standard procedures with a sample size of 10×10×1 cm3 at a heat flux of 35 kW/m2.

Thermogravimetric analysis-infrared spectrometry (TG-IR, FTIR, Nicolet IS50, Thermo Fisher Scien-
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tific, USA; Netzsch, TG 209 F1, Germany) was conducted using a TGA-FTIR coupler from 30 °C to 600

°C at 20 °C/min under air flow of 30 mL/min.

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3. Results and discussion

3.1 Characterization of LDH.

The morphologies and elemental composites of MA-C and MA-P were determined by TEM and

FESEM coupled with EDS. As shown in Fig. S1(a~d), typical and thin 2D layer structure was observed

for the two samples. MA-C displayed well-developed hexagonal nanosheets with a diameter of 20-40 nm

(Fig. S1(a) and (c)), while MA-P showed a layer structure with tiny collapsed edges (Fig. S1(b) and (d)).
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This revealed that the calcination-reconstruction may break the hydrotalcite sheet structure. Compared to

MA-C, EDS analysis of MA-P demonstrated that H2PO4- was successfully intercalated into LDH (Fig.

S1(e) and (f)), which was further confirmed by XRD patterns of MA-C and MA-P. It can be seen from

Fig. S2 that MA-C is highly crystalline and shows the first basal reflection (003) at 2θ=11.71 °, corre-

sponding to the interlayer distance of 0.76 nm. For MA-P, the (003) reflection shifts to 2θ=11.14 °, re-

vealing an increased interlayer distance of 0.79 nm. Also, the occurrence of numerous intense reflections

at lower angle reveals the complete replacement of CO32- by H2PO4-, although MA-C is superior to MA-

P in crystal phase structural integrity and crystallinity (Maarten, E., Ruben, W., Stijn, B., Jon-Petter, G.,

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Dirk, D. V., & Erik, S., 2016).

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3.2 Characterization of cellulose/LDH composite aerogels

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Scheme 1. Schematic illustration of fabrication of flame retardant cellulose/LDH composite aerogels.

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The preparation process of the cellulose/LDH composite aerogels is schematically illustrated in

Scheme 1. Firstly, MgAl-LDH was exfoliated in NaOH/urea solution at -20 ℃ to form stable colloidal

suspensions, in which NaOH hydrates and urea hydrates formed, consequently breaking the original hy-

drogen-bond network between LDH layers and building a new hydrogen-bond network between the hy-

drates and LDH host layers (Wei, Li, & Liu, 2014). Simultaneously, dispersive cellulose macromolecules

as channel inclusion complexes associated with urea, water and NaOH can intercalate into the exfoliated
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LDH nanosheets (Cai et al., 2007; Cai et al, 2008). Finally, stable transparent suspension with LDH and

cellulose was formed. With the incorporation of MBA that can crosslink with cellulose, rigid cellu-

lose/LDH composite aerogels can be formed (Liao et al., 2016).

The morphologies of CA, CAC and CAP were observed by FESEM and shown in Fig. 1. Obviously,

all the aerogels displayed highly hierarchical porous structure even with the incorporation of large amount

of LDH (Fig. 1(a, b, d)). And the porosities of all the composite aerogels were more than 94% with the

increases of MA-C or MA-P contents, although their densities slightly increased (Table S1). This indicated

that LDH nanosheets did not influence the continuous 3D network structure of cellulose aerogels. More-

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over, the effectiveness of LDH blending in cellulose is revealed by Fig. 1(c) and (e), in which the LDH

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nanosheets strongly bond with cellulose phase.

Chemical structures of MA-C, MA-P, CA, CAC-2 and CAP-2 were characterized by FTIR spectra,

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and shown in Fig. S3. In the spectrum of CA, the absorption peaks at 3458 cm-1, 2920 cm-1, 1433 cm-1,

1110 cm-1 and 877 cm-1 are all the characteristic bands of cellulose molecules (Liu et al, 2019). The peak
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at 1634 cm-1 is attributed to the C=O stretching vibration due to the presence of MBA cross-linker (Liao
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et al, 2016). After incorporation with MA-C and MA-P, the shifted peaks at 3440~3445 cm-1 and 1640

cm-1 in CAC-2 and CAP-2 belong to the stretching vibration and the bending vibration of O-H deriving

from interlayer water molecules. New peaks at 500~750 cm-1 are found, which are attributed to the stretch-
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ing vibration of Mg/Al-O. Moreover, the enhanced peak at 1640 cm-1 in CAC-2 is due to interlayer anions

CO32- in MA-C, while the strong peak at 1114 cm-1 in CAP-2 belongs to superimposed peak of P=O and
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P-O (Kim, Jeon, Seo, Dai, & Baek, 2014; Liu, Zhong, Huang, & Li, 2014). All the results revealed the
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introduction of LDH and strong bonding between LDH and cellulose via exfoliation and hydrogen bond-

ing (Liu, Zhong, Huang, & Li, 2014). Washing resistance of the cellulose/LDH composite aerogels also

confirmed the strong bonding between LDH and cellulose matrix. All the aerogels were soaked into water

and stirred for 5 h, no fragments or powders were observed in the bottom of breaker except CAC-1, CAC-

3 and CAP-3, indicating excellent stability and washing resistance of samples (Fig. S4). The negligible

fragments in CAC-1, CAC-3 and CAP-3 can be due to the falling of the sample edges during the stirring.
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Fig. 1. Morphologies of (a) CA, (b, c) CAC-2 and (d, e) CAP-2 with different magnification.

Mechanical properties of cellulose aerogel and cellulose/LDH composite aerogels with different
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LDH loading were assessed through compressive strain-stress curves (Fig. 2a). The compressive behav-

iors of all the aerogels up to 80 % strain are similar, i.e. all aerogels exhibit a linear elastic region below
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10 % strain. Beyond the yield point, a plateau region appears where a large amount of deformation with
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tiny incremental stress occurred owing to the progressive collapse of porous structure in aerogels under

compressive load. Above 60 % strain except CA, CAC-1 and CAP-1, the aerogels display a dramatic

increase in stress derived from the densification of samples after complete collapse of the porous structure.

Obviously, with the increase of LDH amounts, the yield point and the stress hardening stage of the cellu-

lose/LDH composite aerogels moved forward, and the compressive strength improved. Form the Fig. 2b

and 2c, the great crushing resistance of CAC-3 with weight of 0.18 g was observed, which can maintain
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its original state pressed by a beaker (504.98 g) for 30 min. At 80 % strain, the compressive strength of

CA is 0.75 MPa, while the compressive strength reaches up to 1.97 MPa and 2.07 MPa for CAC-3 and

CAP-3, increased by about 2.6 and 2.8 times, respectively, also higher than that of both cellulose/Mg(OH)2

and cellulose/Al(OH)3 composite aerogels (Han, Zhang, Wu, & Lu, 2015; He et al., 2018). Moreover, the

compress modulus of cellulose/LDH composite aerogels is also significantly improved to 63.93 KPa for

CAC-3 and 65.67 KPa for CAP-3 from 0.07 KPa for CA (Fig. S5). These results indicated that the LDH

nanosheets play a crucial role in improving the mechanical property of cellulose aerogel, which may be

derived from the good distribution and strong interfacial bonding between cellulose and LDH via exfoli-

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ation and hydrogen bonding (Liu, Zhong, Huang, & Li, 2014). As mentioned above, LDH nanosheets

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were uniformly distributed in cellulose matrix to form hierarchical porous microstructures, the concen-

trated stress can be dispersed and consumed (Jiang et al., 2018). Thereby, the structural fracture of the

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composite aerogels can be effectually hampered. Simultaneously, the incorporation of LDH induced a

more condensed structure to avoid collapse of the 3D network structure, leading to higher compressive
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strength (Zhu, Chong, Jiang, Liu, & Li, 2019).
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Fig. 2. (a) Compression stress-strain curves of cellulose aerogel and cellulose composite aerogels with

different LDH amounts. Inset is the optical image of CAC-3 undergoing compression test. (b) The optical

image of CAC-3 supporting a beaker weighing 504.98 g. (c) The samples for compression test.

3.3 Thermal stability of cellulose/LDH composite aerogels

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 The thermal-oxidative stabilities of all the cellulose/LDH composite aerogels were evaluated using

thermogravimetric analysis (TGA) and derivative thermograms (DTG) under air atmosphere. The related

data from TGA and DTG, including the decomposition temperature at 10 % (T10%), 75 % (T75%) weight

loss, at the maximum decomposition rate (Tmax), and the elapsed time at 10 % (t10%), 75 % (t75%) weight

loss are presented in Table 1 and Fig. 3. As shown in Fig. 3(a-d), it is known that the initial weight loss

can be due to the water loss before 100 ℃. Compared with CA, the decomposition temperature of cellu-

lose/LDH composite aerogels were slightly decreased. The T10% of CAC-1, CAC-2 and CAC-3 is 238.51

℃, 215.54 ℃, and 217.99 ℃, while 238.38 ℃, 221.45 ℃, and 219.03 ℃ for CAP-1, CAP-2 and CAP-3,

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respectively, lower than that of CA with T10% of 265.60 ℃. The results may be attribute to the removal of

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interlayer H2O of LDH (Liu, Gao, Wang, & Lin, 2018). The main mass loss of all the aerogels occurred

between 220 ℃ to 500 ℃ derived from the decomposition of cellulose and the thermotropic phase transi-

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tion of LDH. Also, the thermal performances of cellulose/LDH composite aerogels are not improved in

comparison with net cellulose aerogels before 330 ℃. Above 330 ℃, the thermal stability of cellulose/LDH
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composite aerogels is obviously improved as well as depends on the LDH contents. The T75% of CAC-1,
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CAC-2 and CAC-3 is 429.54 ℃, 473.94 ℃, and 481.87 ℃, while 428.80 ℃, 469.74 ℃, and 501.57 ℃ for

CAP-1, CAP-2 and CAP-3, respectively, higher than that of CA with T75% of 372.45 ℃. Correspondingly,

t75% of all the cellulose/LDH composite aerogels is prolonged compared to CA and increased as increasing
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LDH contents. Increasing the temperature to 500 ℃, TG curves become flat, while the final residues at

800 ℃ are remarkably different, 6.95 % for CAC-1, 16.48 % for CAC-2, 18.23 % for CAC-3, 7.44 % for
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CAP-1, 19.12 % for CAP-2, 20.11 % for CAP-3, respectively, much higher than that of CA without re-
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sidual.

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Table 1.

TGA data of CA and cellulose composite aerogels with different LDH amounts

Samples T10% (℃) T75% (℃) Tmax (℃) t10% (min) T75% (min) Wres (%)
CA 265.60 372.45 330.22 11.78 17.12 0.00
CAC-1 238.51 429.54 332.87 10.43 18.00 9.95
CAC-2 215.54 473.94 335.44 9.28 22.20 16.48
CAC-3 217.99 481.87 344.26 9.40 22.59 18.23
CAP-1 238.38 428.80 330.95 10.42 19.54 7.44
CAP-2 221.45 469.74 331.62 9.57 22.98 19.12
CAP-3 219.03 501.57 331.95 9.45 23.58 20.11

Because of higher T75%, t75% and residue weight, cellulose/LDH composite aerogels displayed en-

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hanced thermal-oxidative stability. LDH can be effectively exfoliated to nanosheet and uniformly dis-

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persed in cellulose matrix to form a protective layer. During the thermal decomposition process, large

amount of water is released due to LDH absorbed heat and decomposition (Liu, Gao, Wang, & Lin, 2018),

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which is confirmed based on the decomposition process of MA-C and MA-P in Fig. 3e and 3f. Addition-

ally, the decomposition of LDH can generate alumina and magnesia to form dense barrier on the surface
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of cellulose, effectively preventing further the thermal decomposition of cellulose and delaying the weight
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loss (Yu, Wang, O’Hare, & Sun, 2017). Thus, the LDH nanosheets can improve the charring content in

the cellulose aerogel. Compared with CAC, the higher residual mass ratio of CAP can be explained by
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that intercalated H2PO4- may be decomposed to form anhydride acid or pyrophosphoric acid which would

then react with hydroxyl groups of cellulose to form phosphate ester. After dehydration of the phosphate
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ester, a carbon layer will be formed on the surface of cellulose matrix to block the intrusion of external

heat, consequently reducing the combustion of cellulose (Liu, Gao, Wang, & Lin, 2018).
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Fig. 3. (a, c) TGA and (b, d) DTG curves of cellulose aerogel and cellulose composite aerogels with

different LDH amounts under air atmosphere. (e) TGA and (f) DTG curves of MA-C, MA-P, CA, CAC-

2, CAP-2 under air atmosphere.

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3.4 Heat insulation of cellulose/LDH composite aerogels

Table S2 shows the thermal conductivity of representative CA, CAC-2 and CAP-2 samples. The

thermal conductivity of CA is only 0.0371 W/mK, although higher than mixed aerogels of chitosan and

formaldehyde (0.029 W/mK) and cellulose nanofribril (0.0225 W/mK), lower than those of expanded

vermiculite (0.0403 W/mK), SiO2 fiber mat (0.0518 W/mK), and other cellulose aerogel (0.056 W/mK)

(Han, Zhang, Wu, & Lu, 2015; Takeshita and Yoda, 2015; Guo, Chen, Lyu, Fu, & Wang, 2017; Wei, Xie,

Li, & Lin, 2016; Zhang et al., 2018). This may be due to the highly hierarchical porous structure restricting

the phonon propagation in aerogels (Jiang et al., 2018). Introduction of LDH into cellulose matrix, cellu-

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lose/LDH composite aerogels also exhibited prominent heat insulation properties. The thermal conduc-

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tivity of CAC-2 and CAP-2 is 0.0389 W/mK and 0.0370 W/mK, respectively, lower than that of SiO2

composite aerogels with 0.0493 W/mK (Wei, Xie, Li, & Lin, 2016), cellulose/Mg(OH)2 composite aerogel

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with 0.081 W/mK (Han, Zhang, Wu, & Lu, 2015). Moreover, the incorporation of LDH has negligible

influence on the thermal conductivity of cellulose/LDH composite aerogels, because of ignorable change
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in porosity (Table S2). Thus, the cellulose/LDH composite aerogels are promising candidates as green
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insulation materials with improved mechanical strength and thermal stability.

3.5 Combustion behavior of cellulose/LDH composite aerogels

The combustion behavior of cellulose aerogels and cellulose/LDH composite aerogels was evaluated
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by LOI and CONE calorimetry test. Compared with CA with LOI of 18.00 % at 65% RH, the LOI value

of cellulose/LDH composite aerogels progressively increased with the LDH loading, and all are greater
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than 25 % (Fig. 5(a)). Even, the LOI value of CAC-3 and CAP-3 reach up to 35.42 % and 36.25 %,
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respectively, higher than that of other flame retardant loaded cellulose materials, such as cotton fabric

treated by 30-40 % 1-hydroxyethylidene-1,1-diphosphonic acid with LOI of 26.2-29.5 % (Lu et al., 2018),

CNF composite aerogels with LOI of 26.3 % (Guo, Chen, Lyu, Fu, & Wang, 2017). In addition, it can be

found from Fig S6 that all the aerogels exhibited the increased LOI values with the increases of ambient

humidity, making the ignition of aerogels more difficult. The effect of humidity on the physicochemical

properties of cellulose aerogels will be further investigated systematically in our following work.
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 Further, representative CA, CAC-2 and CAP-2 was used to investigate the flame retardancy prop-

erties by CONE calorimetry test. CA can quickly ignite after 4 s with burning time of 43 s (Table 2, Fig.

S7 and Video S1). Compared with CA, the cellulose/LDH composite aerogels are flame retardant and are

easier to extinguish due to their relatively long Tignition and short Tburning (Table 2 and Fig. S7). The heat

release rate (HRR) of different samples is shown in Fig. 4(a). CA displayed sharp twin peaks with the

peak of heat release (PHRR) of 116.34 kW/m2, revealing an inflammability of cellulose aerogels. In con-

trast, the sharp twin peaks for CAC-2 and CAP-2 apparently converged and reduced with smaller PHRR

values of 68.61 kW/m2 and 58.51 kW/m2, respectively. Obviously, PHRR can be reduced by 41 % and 50

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% due to the incorporation of MA-C and MA-P, respectively. Also, introducing LDH in cellulose aerogel,

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the time to peak heat release (tPHRR) of the CAC-2 and CAP-2 was delayed to 25 s and 20 s, respectively.

For the sharp twin peaks of CA, it burns severely, and releases large amount of heat in a short time (tPHRR

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of 15 s). For obviously reduced peak of CAC-2 and CAP-2, LDH is decomposed, large amount of water

is released and absorbed heat, as well as the generated alumina and magnesia can reduce the heat transfer
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from flame zone to sample, inhibiting the release of inner pyrolysis products (Gao, Wu, Wang, Charles,
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& O.Hare, 2014).

Table 2.
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Cone calorimeter data of CA, CAC-2 and CAP-2

Sample Tignition Tburning PHRR TPHRR THR

PEHC (MJ*Kg-1)
name (S) (S) (kW*(m2)-1) (S) (MJ*m2)
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CA 4 43 116.34 15 5.17 45.17

CAC-2 11 14 68.61 25 4.06 38.85
CAP-2 9 9 58.51 20 5.22 26.99
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Fig. 4(b) shows the total heat release (THR) curve of CA, CAC-2 and CAP-2, which is determined

by the mass of the sample and the decomposition products (Gao, Wu, Wang, Charles, & O.Hare, 2014).

For CA and CAC-2, fast increment in heat release in the first stage, then more gradual heat release was

observed. While a continuous increase in heat release for CAP-2 was shown. Compared with CA, THR

values of CAC-2 and CAP-2 were lower during combustion. Additionally, the maximum THR value of

CA was 5.17 MJ/m2 within a given time period, while 4.06 MJ/m2 for CAC-2, 5.22 MJ/m2 for CAP-2,

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respectively. It was observed that THR value of CAP-2 did not change obviously compared with that of

CA, because MA-P has worse heat absorption capacity than MA-C. As shown in Fig. 3(e), the thermal

decomposition behavior of MA-C and MA-P is obviously different. MA-C shows thermal decomposition

behavior in the whole process, while the thermal decomposition process of MA-P mainly occurs when the

temperature is under 350 ℃ and basically does not decompose in the later stage. As a result, in the late

stage of cellulose combustion, its heat absorption capacity is poor, which has little influence on the heat

release of cellulose combustion. The heat released by MA-P is more than the heat absorbed by MA-C.

Finally, the THR of CAP-2 is slightly larger than CAC. To avoid the mass differences from the compari-

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son, the effective heat of combustion (EHC) was calculated by the ratio of THR to the mass of the aerogels.

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Compared with the CA, the EHC peaks (PEHC) of CAC-2 and CAP-2 decreased by 14 % and 40 % (Table

2), respectively, indicating a formation of dense char layer to suppress the decomposition of cellulose

matrix.

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Smoke production ratio (SPR) is also an important parameter in fire safety fields. From Fig. 4(c), it
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is clearly that CA exhibited a sharp SPR peak (PSPR) of 0.053 m2/s at 20.5 s, revealing that CA released
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a large amount of smoke during combustion. Compared with CA, the SPR curve of CAP-2 dramatically

decreased with a SPR peak value of 0.011 m2/s, 79 % reduction. While, the SPR curve of CAC-2 is notably

different with three SPR peaks during burning process. And the SPR peak value was reduced by 75 %, 70
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% and 72 %. All the data indicated that the incorporation of LDH can suppress the generation of smoke

of cellulose/LDH composite aerogels. After ignition, the cellulose composite aerogel rapidly decomposes
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gaseous small molecular hydrocarbons and free radicals by high temperature, and covalently bonds incip-
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ient particles formed with the chain initiation and chain growth. Then the particles regenerate resonance-

stabilized radicals after a series of hydrogen evolution reactions, while the continuous growth of the res-

onance-stabilized radicals on surface and cluster eventually lead to the formation of visible smoke (Jo-

hansson, Head-Gordon, Schrader, Wilson, & Michelsen, 2018). LDH itself has microporous structure and

large specific surface area, therefor it can absorb small smoke particles (Yu, Wang, O’Hare, & Sun, 2017).

At the same time, LDO formed after decomposition also has micropores structure, which adheres to the
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surface of the cellulose to form a barrier and retain the smoke particles in the condensed phase to play a

role in smoke suppression (Xu, Wang, Lia, & Wang, 2015). Furthermore, because of the promoted car-

bonation ability of H2PO4-, MA-P is beneficial to inhibit the formation of resonance-stabilized radical

particles, consequently exhibiting a better effect of smoke suppression (Maryam, Federico, Per, & Lars,

2015).

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Fig. 4. (a) HRR, (b) THR, (c) SPR, and (d) MLR plots of CA, CAC-2, and CAP-2. Inset is the optical
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images of CA, CAC-2, and CAP-2.

Mass loss rate (MLR) is another parameter for fire safety, which imply the thermal stability of sam-

ples when burning. As shown in Fig. 4(d), the trend of MLR curve of CA is different from CAC-2 and

CAP-2, and the trend of CA is rapidly growing from -0.41 g/s in 9.77 s, earlier than the time of PHRR

and PSPR. Relatively, the trend of CAC-2 and CAP-2 are all down at first, then they all trend to zero

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finally, and the total variation of them is clearly smaller than CA. The result means the thermal stability

of CAC-2 is better than CA and CAP-2, and the CA’s is the worst. The insets show that CA shrunken and

carbonized significantly after cone calorimetry test, while CAC-2 and CAP-2 just broken down, which

also indicated that the thermal stability of CA is worse than CAC-2 and CAP-2. It is because that LDH

nanosheets wrap and arrange along cellulose molecular chain, and play a role in structural support, thereby

preventing the collapse of the composite aerogels after combustion. On the other hand, LDH covered the

surface of cellulose molecules and inhibited the reaction between the radicals generated during pyrolysis,

blocking the formation and growth of carbon nuclei, consequently producing white residue (Johansson,

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Head-Gordon, Schrader, Wilson, & Michelsen, 2018).

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3.6 Risk factor analysis of cellulose/LDH composite aerogels

Further, fire performance index (FPI) and fire growth index (FGI) are often used to evaluate the fire

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risk of the flame-retardant materials. FPI is computed by the ratio of tignition to PHRR, reflects the flashover

time. FGI indicates the material size on the thermal reaction ability, is defined by the ratio of PHRR to
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the corresponding peak time (He et al., 2018). As shown in Fig. 5(b), the FPI and FGI of CA is 0.034 and
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7.75, revealing that CA has a great threat to human safety. Introducing LDH in cellulose aerogel, FPI of

CAC-2 and CAP-2 obviously increased to 0.16 and 0.15, while FGI reduced to 2.74 and 2.93, respectively.

These results confirmed that the LDH can significantly improve the flame retardancy on cellulose aero-
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gels. And CAC-2 displays the highest FPI and lowest FGI, showing that MA-C can offer higher safety

rank than MA-P due to the low PHRR and the longest ignition time of CAC-2.
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3.7 Microstructure of residual char

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The microstructure of residual char after CONE calorimetry test was further observed by FE-SEM,

and presented in Fig. 5(c~h). Neat CA carbonized, shrank (Inset in Fig. 4d), and the char is thin and fluffy,

like paper ash (Fig. 5(c) and (d)). The char of CAC-2 is relatively strong, but porous structure was found,

resulting from the releases of a large of water vapor and CO2 during the combustion of cellulose and MA-

C. Differently, the char layer of CAP-2 possessed a compact and continuous surface, as well as caked,

which might be due to the rapid formation of char promoted by H2PO4- (Maryam, Federico, Per, & Lars,
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2015). The dense char layer can prevent fuel volatilization and hamper heat and O2 feedback, resulting in

excellent flame resistance. Also, LDO formed during decomposition acted as a heat barrier, inhibiting the

fire spread, meanwhile adsorbed the decomposition products generating from cellulose aerogel.

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Fig. 5. (a) Limiting oxygen index of cellulose aerogel and cellulose composite aerogels with different

LDH amounts, (b) FGI and FPI values of CA, CAC-2, and CAP-2. (c~h) FESEM images of residues char

of CA (c, d), CAC-2 (b, e), and CAP-2 (c, f) with different magnification.

3.8 TG-FTIR analysis

20
 To get a deeper understanding of the flame retardant mechanism, TGA-FTIR was used to investigate

the gaseous products at different thermal degradation temperatures. The 3D TGA-FTIR spectra of pyrol-

ysis products of CA, CAC-2 and CAP-2 were shown in Fig. 6. It can be found that the gaseous products

display characteristic bands at 3730-3550 cm-1, 2400-2200 cm-1, 1850-1600 cm-1, 680-660 cm-1, attrib-

uting to H2O, CO2, CO, and carbonyl gaseous compounds, indicating the main pyrolysis products are

H2O, CO, CO2, and aldehyde/ketone carbonyl gaseous compounds. For CA and CAC-2, the peak signal

of pyrolysis products gradually increases with the increase in temperature. While, the thermal decompo-

sition process of CAP-2 is obviously different. With the increase in temperature, the characteristic bands

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of H2O at 3730-3550 cm-1 and carbonyl gaseous compounds at 1850-1600 cm-1 gradually reduced. The

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peak signal at 2400-2300 cm-1 and 680-660 cm-1 is relatively strong, but declines after 480 ℃. It implied

that the thermal decomposition of CAP-2 occur at early stage (below 480 ℃) due to the incorporation of

MA-P, which fits well the results of TGA in Fig. 3(e & f).

3.9 Flame retardant mechanism -p

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LDH is a new type of inorganic flame retardant, that can absorb a mass of generated heat to reduce
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the surface temperature of polymer matrix, H2O and CO2 gases released during the decomposition process

can dilute the combustible gas and hinder the contact of combustible gas with matrix, consequently de-

laying the pyrolysis and decomposition rate. At the same time, generated metal oxides (LDO) during the
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LDH thermal decomposition not only can adsorb harmful gases from material combustion, but also can

react with the pyrolysis products of polymer to form carbon layer to further cut off the intrusion of heat
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and oxygen (Liu, Gao, Wang, & Lin, 2018; Gao, Wu, Wang, Charles, & O.Hare, 2014). In this work,
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MgAl-LDHs were incorporated with cellulose aerogels in which the interlayer anion of LDH is varied by

CO32- and H2PO4-. The reduced PHRR, PEHC and SPR upon the introduction of LDH into cellulose aer-

ogel revealed the gas-phase flame retardant mechanism. Compared to neat CA, the increased mass of

residual char of CAC and CAP samples confirmed the coexistence of condensed phase flame retardant

mechanism. Moreover, CAC and CAP samples exhibited different thermal performances. CAC displayed

good fire resistance due to its longer ignition time of 11 s, while CAP has excellent self-extinguishing
21
ability (Table 2). Moreover, CAP samples exhibited obviously reduced PHRR, PEHC and SPR, while

CAC samples have higher safety rank owing to the highest FPI and lowest FGI (Fig. 5(b)). The difference

in flame retardancy of CAC and CAP may be resulted from the different thermal properties of MA-C and

MA-P (Fig. 3(e & f)). Compared to MA-C, the imperfect crystal structure of MA-P originated from the

calcination-reconstruction process make its susceptible to heat, consequently easily being ignited. The

generated pyrophosphoric acid can catalyze the char formation which protects the underlying matrix from

heat and shields the fuel gases released from the surface (Xu et al., 2017). The proposed flame retardant

mechanisms of the aerogels were illustrated in Scheme 2.

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CAP-2

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Fig. 6. TGA-FTIR spectra of (a) CA, (b) CAC-2, and (c) CAP-2 in air flow.

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Scheme 2. proposed flame retardant mechanism of cellulose composite aerogels incorporated with LDH.

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4. Conclusions

In summary, high performance cellulose composite aerogels were successfully fabricated by incor-
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porating MgAl-LDH with cellulose via a facile cosolvent exfoliation of LDH. The resultant cellulose

composite aerogels have a hierarchical interconnected 3D porous network with porosity more than 94 %.
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The exfoliated LDH uniformly dispersed in cellulose matrix and has strong bonding with cellulose. Con-

sequently, CAC-2 and CAP-2 displayed high compression strength, increased by 2.6 and 2.8 times com-
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pared with CA at 80 % strain, respectively. Moreover, CAC-2 and CAP-2 showed outstanding flame re-

tardant and smoke suppression performances, PHRR was reduced by 41 % and 50 %, as well as the re-
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duction in SPR was 79 % and 75 %, respectively. Additionally, the cellulose composite aerogels showed
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high safety rank, and excellent thermal insulation. According to the cone calorimeter test and TG-FTIR

analysis, the outstanding flame retardancy and smoke suppression of the cellulose composite aerogels

were mainly due to the dilution effect of LDH for combustible gas because of H2O and CO2 gas release,

as well as the physical barrier and carbonization effect of LDH, i.e. dual gas-phase and condensed phase

flame retardant mechanisms. This work provides an important approach for developing high-performance

23
cellulose aerogels with outstanding mechanical strength, flame retardant, smoke suppression and thermal

insulation, which are promising substitutes in green advanced engineering filed.

Authors’ contributions
Xiaolei Luo and Lin Liu conceived and designed the study. Xiaolei Luo, Junyan Shen, Yanan
Ma, and Ranju Meng performed the experiments. Xiaolei Luo wrote the paper. Lin Liu, Juming Yao
and Xiaolei Luo reviewed and edited the manuscript. All authors read and approved the manuscript.

Acknowledgment

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The work was financially supported by the Public Technology Research Plan of Zhejiang Province

(No. LGF18E030003), National Natural Science Foundation of China (No. 51672251), and the Funda-

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mental Research Funds of Zhejiang Sci-Tech University (2019Q008).

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References

Cai, J., Zhang, L. N., Chang, C. Y., Cheng, G. Z., Chen, X. M., & Chu, B. (2007). Hydrogen-bond-induced

inclusion complex in aqueous cellulose/LiOH/urea solutionat low temperature. Physical Chemistry

Chemical Physics, 8, 1572-1579.

Cai, J., Zhang, L. N., Liu S. L., Liu, Y. T., Xu, X. J., Chen, X. M. et al. (2008). Dynamic self-assembly

induced rapid dissolution of cellulose at low temperatures. Macromolecules, 41(23), 9345-9351.

Chen, W.S., Yu, H.P., Lee, S.Y., Wei, T., Lia, J., & Fan, Z.J., (2018). Nanocellulose: a promising nano-

material for advanced electrochemical energy storage. Chemical Society Reviews, 47, 2837-2872.

of
Fernades, E.M., Pires, R.A., Mano, J.F., & Reis, R.L. (2013). Bionanocomposites from lignocellulosic

ro
resources: properties, applications and future trends for their use in the biomedical field. Polymer

Science, 38, 1415-1441.

-p
Fu, Q. L., Medina, L. L., Li, Y. Y., Federico, C., Alireza, H. L., & Lars, A. B. (2017). Nanostructured

wood hybrids for fire-retardancy prepared by clay impregnation into the cell wall. ACS Applied Ma-
re
terials & Interfaces, 9, 36154-36163.
lP

Gao, Y. S., Wu, J. W., Wang, Q., Charles, A. W., & O.Hare, D. (2014). Flame retardant polymer/layered

double hydroxide nanocomposites. Journal of Materials Chemistry A, 2, 10996-11016.

Guo, L. M., Chen Z. l., Lyu S., Fu, F., & Wang, S. Q. (2017). Highly flexible cross-linked cellulose nan-
na

ofibril sponge-like aerogels with improved mechanical property and enhanced flame retardancy. Car-

bohydrate Polymer, 179, 333-340.

ur

Han, Y. Y., Zhang, X. X., Wu, X. D., & Lu C. H. (2015). Flame retardant, heat insulating cellulose aerogels
Jo

from waste cotton fabrics by in situ formation of magnesium hydroxide nanoparticles in cellulose

gel nanostructures. ACS Sustainable Chemistry & Engineering, 3, 1853-1859.

He, C. L., Huang, J. Y., Li, S. H., Meng, K., Zhang, L. Y., Chen, Z. et al. (2018). Mechanically resistant

and sustainable cellulose-based composite aerogels with excellent flame retardant, sound-absorption,

and superantiwetting ability for advanced engineering materials. ACS Sustainable Chemistry & En-

gineering, 6, 927-936.
25
Imre, B., Garcia, L., Puglia, D., & Vilaplana, F. (2019). Reactive compatibilization of plant polysaccha-

rides and biobased polymers: review on current strategies, expectations and reality. Carbohydrate

Polymer, 209, 20-37.

Jiang, F., Li, T., Li, Y. J., Zhang, Y., Gong, A., Dai, J. Q. et al. (2018). Wood-based nanotechnologies

toward sustainability. Advanced Materials, 30, 1703453.

Johansson, K. O., Head-Gordon, M. P., Schrader, P. E., Wilson, K. R., Michelsen, H. A. (2018). Reso-

nance-stabilized hydrocarbonradical chain reactions may explain soot inception and growth. Science,

361, 997-1000.

of
Kiliaris P. & Papaspyrides C. D. (2010). Polymer/layered silicate(clay) nanocomposites: an overview of

ro
flame retardancy. Polymer Science, 35(7), 902-958.

Kim, M. J., Jeon, I. Y., Seo, J. M., Dai, L. M., & Baek, J. B. (2014). Graphene phosphonic acid as an

efficient flame retardant. ACS Nano, 8(3), 2820-2825.

-p
Li, C., Wan, J. T., Kalali, E. N., Fan, H., & Wang, E. L. (2015). Synthesis and characterization of functional
re
eugenol derivative based layered double hydroxide and its use as a nanoflame-retardant in epoxy
lP

resin. Journal of Materials Chemisry A, 3, 3471-3479.

Liao, Q., Su, X. P., Zhu, W. J., Hua, W., Qian, Z. Q., Liu, L. et al. (2016). Flexible and durable cellulose

aerogels for highly effective oil/water separation. RSC Advances, 6, 63773-63781.

na

Liu, R. T., Chi, L.N., Wang, X. Z., Wang, Y., Sui, Y. M., & Xie, T. T. et al. (2019). Effective and selective

adsorption of phosphate from aqueous solution via trivalent-metals-based amino-MIL-101 MOFs.

ur

Chem. Eng. J. 357, 159-168.

Jo

Liu, C. Y., Zhong, G. J., Huang, H. D., & Li Z. M. (2014). Phase assembly-induced transition of three

dimensional nanofibril- to sheet-networks in porous cellulose with tunable properties. Cellulose, 21,

383-394.

Liu, Y., Gao, Y. S., Wang, Q., & Lin, W. R. (2018). The synergistic effect of layered double hydroxides

with other flame retardant additives for polymer nanocomposites: a critical review. Dalton Transac-

tions, 47, 14827-14840.

26
Lu, Y., Jia, Y. L., Zhou, Y., Zou, J., Zhang, G. G., & Zhang, F. X. (2018). Straightforward one-step solvent-

free synthesis of the flame retardant for cotton with excellent efficiency and durability. Carbohydrate

Polymer, 201, 438-445.

Maarten, E., Ruben, W., Stijn, B., Jon-Petter, G., Dirk, D. V., & Erik, S. (2006). Phosphate-exchanged

Mg-Al layered double hydroxides: a new slow release phosphate fertilizer. ACS Sustainable Chem-

istry & Engineering, 4, 4280-4287.

Maryam, G., Federico, C., Per, T. L., & Lars, W. (2015). Phosphorylated cellulose nanofibrils: a renewable

nanomaterial for the preparation of intrinsically flame-retardant materials. Biomacromolecules, 16,

of
3399-3410.

ro
Ramage, M.H., Burridge, H., Busse-Wicher, M., Fereday, G., Reynolds, T.P.S., Shah, D.U., et al. (2017).

The wood from the trees: the use of timber in construction. Renewable & Sustainable Energy Reviews,

68, 333-359.

-p
Ren, W. J., Gao, J. K., Lei, C., Xie, Y. B., Cai, Y. R., Ni, Q. Q., et al. (2018). Recyclable metal-organic
re
framework/cellulose aerogels for activating peroxymonosulfate to degrade organic pollutants. Chem-
lP

ical Engineering Journal, 34, 766-774.

Takeshita, S. & Yoda, S. (2015). Chitosan aerogels: transparent, flexible thermal insulators. Chemistry of

Materials, 27, 7569-7572.

na

Wang, Q., Undrell, J. P., Gao, Y S., Cai, G. P., Buffet, J. C., Wilkie, C. A., et al. (2013). Synthesis of flame-

retardant oolypropylene/LDH-borate nanocomposites. Macromolecules, 46, 6145-6150.

ur

Wang, S., Lu, A., & Zhang, L.N. (2016). Recent advances in regenerated cellulose materials. Progress in
Jo

Polymer Science, 53, 169-206.

Wang, Y. T., Zhao, H. B., Degracia, K., Han, L. X., Sun, H., Sun, M. Z., et al. (2017). Schiraldi, Green

approach to improving the strength and flame retardancy of poly(vinyl alcohol)/clay aerogels: incor-

porating biobased gelatin. ACS Applied Materials & Interfaces, 9, 42258-42265.

27
Wei, H. T., Xie, X. Z., Li, X. Q., & Lin, X. S. (2016). Preparation and characterization of capric-myristic-

stearic acid eutectic mixture/modified expanded vermiculite composite as a form-stable phase

change material. Applied Energy, 178, 616-623.

Wei, Y., Li, F. C., & Liu, L. (2014). Liquid exfoliation of Zn-Al layered double hydroxide using

NaOH/urea aqueous solution at low temperature. RSC Advances, 4, 18044-18051.

Xu, L. L.; Xiao, L. H.; Jia, P.; Karel, G.; Liu, P.; Li, H. et al. (2017). Lightweight and ultrastrong polymer

foams with unusually superior flame retardancy. ACS Applied Materials & Interfaces, 9, 26392-

26399.

of
Xu, W. Z., Wang, S. Q., Lia, A. J. & Wang, X. L. (2015). Synthesis of aminopropyltriethoxysilane

ro
grafted/tripolyphosphate intercalated ZnAl LDHs and their performance in the flame retardancy and

smoke suppression of polyurethane elastomer. RSC Advances, 6, 48189-48198.

-p
Xu, W. Z., Zhang, B. L., Wang, X. L., Wang, G. S., & Ding, D. (2018). The flame retardancy and smoke

suppression effect of a hybrid containing CuMoO4 modified reduced graphene oxide/layered double
re
hydroxide on epoxy resin. Journal of Hazardous Materials, 343, 364-375.
lP

Ye, D.D., Yang, P.C., Lei, X.J., Zhang, D.H., Li, L.B., Sun, P.C., et al. (2018). Robust anisotropic cellulose

hydrogels fabricated via strong selfaggregation forces for cardiomyocytes unidirectional growth.

Chemistry of Materials, 30, 5175-5183.

na

Yu, J. F., Wang, Q., O'Hare, D., & Sun, L. Y. (2017). Preparation of two dimensional layered double

hydroxide nanosheets and their applications. Chemical Society Reviews, 46, 5950-5974.
ur

Zhang, H., Zhang, C., Ji, W. T., Wang, X., Li, Y. M., & Tao, W. Q. (2018). Experimental characterization
Jo

of the thermalconductivity and microstructure of opacifier-fiber-aerogel composite. Molecules, 23,

2198.

Zhu, J. D., Chong, J. H., Jiang, W., Liu, Y., & Li, Y. (2019). Ultralight, hydrophobic, monolithic konjac

glucomannan-silica composite aerogel with thermal insulation and mechanical properties. Carbohy-

drate Polymer, 207, 246-255.

28