Journal of Sol-Gel Science and Technology

Multi-scale hybrid aerogel composites reinforced with aramid fiber fabric for thermal
protection field
--Manuscript Draft--

Manuscript Number: JSST-D-21-00698

Full Title: Multi-scale hybrid aerogel composites reinforced with aramid fiber fabric for thermal
protection field

Article Type: Original Paper

Keywords: Eco-friendly; Multi-scale; Aramid fiber fabric; Hybrid silica aerogel; Thermal
protection performance

Abstract: An eco-friendly and multi-scale hybrid method for improving the thermal protection
performance of protective materials in high temperature flame environment was
provided. The aramid fiber fabric reinforced hybrid silica aerogel composite (AF-HSiO2)
was prepared by the two-step sol-gel method using AF nonwovens as the three-
dimensional reinforced materials, deionized water as the sole solvent and HSiO2
aerogel as the growth substrate followed by freeze-drying method (FD). The resulted
composites perfectly owned their nano porous structure and excellent properties of
high porous (81.12%), low bulk density (0.1612 g cm-3) and large surface area (659
m2 g-1). In addition, when the composite was exposed to a high heat flux of 84 ± 2 kW
m-2, the thermal protection performance increased by 27.97% compared with the
commercial thermal liner of fire-fighting clothing. The nature also endowed the
composites with tensile strength (319.2 N) and hydrophobic angle (136°). These
favorable multi-features indicate that composites have broad prospects in thermal
protection filed.

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2 Multi-scale hybrid aerogel composites reinforced with aramid fiber fabric for thermal protection field
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5 Shengnan Zhai1,2, Hongbo Wang1,2, ⁎ , Jiajia Fu1,2, ⁎ , Kejing Yu3, Chaoran Meng1,2
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7 1
Jiangsu Engineering Technology Research Centre of Functional Textiles, Jiangnan University, Wuxi
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10 214122, China;
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13 Education Ministry Ley Laboratory of Science & Technology for Eco-textiles, Jiangnan University,
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16 Wuxi 214122, China.
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18 3
Key Laboratory of Eco-Textile of Ministry of Education, Jiangnan University, Wuxi 214122, China;
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21 Abstract
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24 An eco-friendly and multi-scale hybrid method for improving the thermal protection performance of
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27 protective materials in high temperature flame environment was provided. The aramid fiber fabric
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29 reinforced hybrid silica aerogel composite (AF-HSiO2) was prepared by the two-step sol-gel method using
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32 AF nonwovens as the three-dimensional reinforced materials, deionized water as the sole solvent and HSiO2
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35 aerogel as the growth substrate followed by freeze-drying method (FD). The resulted composites perfectly
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38 owned their nano porous structure and excellent properties of high porous (81.12%), low bulk density
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40 (0.1612 g cm-3) and large surface area (659 m2 g-1). In addition, when the composite was exposed to a high
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43 heat flux of 84 ± 2 kW m-2, the thermal protection performance increased by 27.97% compared with the
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46 commercial thermal liner of fire-fighting clothing. The nature also endowed the composites with tensile
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49 strength (319.2 N) and hydrophobic angle (136°). These favorable multi-features indicate that composites
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have broad prospects in thermal protection filed.
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54 Keywords
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57 Eco-friendly; Multi-scale; Aramid fiber fabric; Hybrid silica aerogel; Thermal protection performance;
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*Corresponding Author:
62 E-mail addresses: wxwanghb@163.com (H. Wang); jiajiafu@jiangnan.edu.cn (J. Fu).
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 1
2 Highlights
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4 1. In the freeze-drying system, deionized water was the only solvent, aramid fiber (AF) reinforced silica
5 aerogel composites were prepared by sol-gel method using methyltrimethoxysilane (MTMS) and
6
7 water-glass as co-precursors.
8 2. It was found that the volume of silica sol, especially the molar ratio of co-precursors, had profound
9 influences on the properties of the composites.
10
11 3. The resulted composites owned the excellent properties, leading to the remarkable thermal protection
12 performance, which is increased by 27.97% compared with the thermal insulation lining of commercial
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14 fire-fighting clothing, in which the TPP value is 11.36 cal/cm2 and the second degree burn time is 5.82
15 s.
16 4. The nature also endowed the composites with tensile strength (319.2 N) and hydrophobic angle (136°).
17
18 1. Introduction
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21 With the development of social economy, the probability of fire accidents increases gradually, which
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24 seriously threatens the life safety of personnel. It puts forward higher requirements for the thermal
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27 protective performance of materials. Silica aerogel is a kind of excellent insulating material (λ < 0.02 W
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29 m−1 K−1) which is widely concerned by scientists. It has also attracted substantial attention in aerospace,
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32 industry, construction and many other fields, etc. [1] . However, silica aerogels are usually of low strength,
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35 fragility and brittleness, due to the neck structure formed by weak interfacial interaction between
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38 nanoparticles in silica aerogel network [2]. Therefore, in order to meet the high-level requirements for the
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40 mechanical properties [3], it has practical significance to synthesize aerogels with excellent thermal
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43 protective performance and mechanical properties.
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46 In recent years, mechanical behaviors of silica aerogel materials have been enhanced by various
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49 approaches[4,5]. The most effective one among these approaches method is to use fiber network as support
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skeleton [6,7], especially low-density fiber fabric[8-10], which attributed to the high transmittance of silica
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54 aerogels to near infrared radiation (2.5-8 um) in high temperature and the flammability of organic
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57 components (Si-OR and Si-R)[11]. The low-density fabrics with excellent thermal-resistance and flame
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61 2
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 1
2 retardancy, as well as excellent mechanical properties at high temperature [12] can be served for three-
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5 dimensional (3D) porous reinforced materials to improve the multiple functions of silica aerogels[13].
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7 Hence, in order to achieve better thermal protection performance in high temperature flame environment,
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10 we propose a method for constructing multi-scale hybrid aerogel composites, which consist of reinforcing
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13 material and hybrid aerogel matrix. In addition, to avoid the lengthy solvent exchange process and harmful
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16 organic solvents, the method of using deionized water as the only solvent instead of organic solvent is
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18 further proposed.
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21 Therefore, in this experiment, deionized water was used as the only solvent, MTMS and water-glass as
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24 the co-precursor, the AF-HSiO2 aerogel composites were achieved by using AF nonwovens as three-
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27 dimensional growth templates to further grow hybrid silica network structure through hydrolysis
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29 polycondensation followed by FD. Furthermore, based on the previous research of the group, effects of the
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32 volume of silica sol, especially the molar ratio of co-precursors on the properties of aerogels were
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35 emphatically investigated.
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38 2. Experimental
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40 2.1. Materials
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43 Aramid fiber needle felt (AF) used as reinforcements were purchased from SWOTO. Water glass (wt.:
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46 34.2%, Na2O::SiO2 = 1:: 3.28) and MTMS used as co-precursors were provided by Guangzhou Huixin
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49 Chemical CO, Ltd. (China) and Aladdin. Other agents such as hydrochloric acid and ammonia used as acid-
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base catalysts were purchased from Sinopharm Chemical Reagent Co., Ltd. (China). Deionized water used
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54 as solvent was made in the laboratory. All reagents were used at the analytical level.
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57 2.2. Synthesis of hybrid silica aerogels
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 1
2 The stepwise experimental process is illustrated in Figure1(a). The first step was the preparation of co-
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5 precursor silica sol, which required the hydrolysis of the two precursors separately. The water glass was
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7 first mixed with deionized water in the volume ratio of 1:4, and then 0.5 mol L-1 hydrochloric acid was
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10 added and the pH of the solution was adjusted to 2.0. After 24 h, the MTMS was mixed with hydrochloric
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13 acid (0.5 M) and deionized water in a molar ratio of 1:40:1.45×10-3 for 30 min, and then bathed in water at
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16 45 ℃ for 30 min. Thus, the co-precursor silica sol could be obtained by mixing the above two solutions for
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18 10 min and adding NH4OH solution (1M) to adjust the pH to 6.30. The molar ratio of MTMS/water glass
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21 was defined as X, and the values of X were 0, 1.0, 1.5, 2.0 and 2.9, respectively.
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24 2.3. Preparation of AF-HSi aerogel composite
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27 The resulting co-precursor alcosol was quickly poured into the mold, and the AF fabric (0.10 g) was
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29 completely immersed in the alcosol with the volume of 0.75 ml, 1.80 ml, 2.50 ml and 3.0 ml. Then the
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32 condensation occurred and the gel generally formed in 20 min at 45 ℃ in water bath. The mold was sealed
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35 with deionized water and aged for 24 h at 45 ℃ in water bath. Later, the aged gel was frozen in the
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38 refrigerator and dried in vacuum for 48 h in a laboratory freeze dryer.
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40 2.4. Characterization
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43 The bulk density of the AF/aerogels was calculated based on its weight to volume ratio. The porosity
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46 was then calculated by formula (A.1) [14]. Where, ρb is the density of the AF/aerogels, ρs is the density of
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49 silica skeleton (2.19 g cm-3, 25 °CW, 1 atm), and ρf is the density of the reinforced fiber (1.40 g cm-3). The
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microstructure was studied by field emission scanning electron microscope (FE-SEM, SU8220, FEI). The
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54 specific surface areas were estimated by BET method, while the pore size distribution was calculated by
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57 BJH method (Tristar II 3020M, Micromeritics Instrument Corporation, USA).
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 1
2 The chemical structure of composites was illustrated by measuring the infrared spectra within the
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5 wavelength range of 500-4000 cm-1 (FTIR, Nicolet is10, Seymour Fisher Technology (China) Co.,
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7 LTD). The hydrophobicity was obtained by measuring the contact angle (θ) of a water droplet (10 ul)
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10 on the surface of samples (DSA 100, Krüss, Germany). The tensile strength was investigated by
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13 stretching the material at a rate of 100 mm/min (HD026NS). The thermal stability was characterized
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16 by measuring the weight loss of samples from room temperature to 800 ℃ with a heating rate of
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18 10 ℃/min (TGA Q550). The thermal protection performance was obtained by testing the second
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21 degree burn time and TPP value under heat flux of 84±2 kW m-2 (#403-14, Thermetrics, USA).
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24 2. Results and discussion
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28 3.1. Morphological characterizations of the AF-HSiO2 composites
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32 the AF-HSiO2 aerogel composites were realized by using AF nonwovens as three-dimensional growth
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templates to further grow hybrid silica network structure through hydrolysis polycondensation followed by
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37 FD. Nanoscale silica aerogel particles adhered tightly to the aramid fiber matrix and still maintained the
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40 three-dimensional nanoporous structure (shown in Figure 1(b)). The AF with density of 0.1307 g cm-3 and
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43 porosity of 84.43% adopted herein were acted as supporting skeleton, which were just a physical
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combination with silica aerogels [15]. Thus, the main chemical reactions in the procedure were the
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48 hydrolysis and condensation of co-precursors. It could be seen from equation (B.1) and (B.2) that the Si
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51 (OH)4 molecules with hydroxyl groups on the surface were formed by sufficient hydrolysis of water glass,
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54 while MTMS still retained a non hydrolyzable CH3 group. Then the gel skeleton was initially formed during
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the process of condensation, just as described in equation (B.3) and (B.4). The secondary particles with
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59 large numbers of hydroxyl groups on the surface were obtained by the condensation of these Si(OH) 4
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 1
2 molecules, whereas in the presence of MTMS, the non-polar group (-CH3) on the surface led to the
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5 formation of relatively small secondary particles [7]. Finally, these two secondary particles formed silica
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7 (SiO2) and polymethylsilsesquioxane (PMSQ) gel network respectively (as shown in Figure 1(b), a dense
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10 arrangement of larger particles was observed in SiO2 network, while clusters and larger pores were observed
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13 in PMSQ network caused by polar Si-CH3 groups [7]). This could be confirmed by FTIR.
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16 Figure 1(c) presents the FTIR of AF, AF-SiO2 and AF-PMSQ aerogel composites. In the FTIR spectrum
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18 of the sample AF-SiO2, the characteristic vibrations of the SiO2 resulted from water glass hydrolysis and
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21 polycondensation appeared at 1069 cm−1 and 776 cm-1 generated by the stretching vibrations of Si-O-Si
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24 bonds [16], and 964 cm−1 generated by Si-OH vibrations [17]. In the FTIR spectrum of the sample AF-
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27 PMSQ, the Si-OH groups were replaced by Si-CH3 groups produced by MTMS hydrolysis, and
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29 corresponding vibration bands were generated at 1275 cm−1 and 910 cm−1 [18]. In addition, the introduction
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32 of MTMS was equal to the conventional surface modification so that the problem of capillary pressure to
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35 the nanopores during drying process could be ignored [19].
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38 In order to further illustrate the porous structure of silica aerogels prepared with pure water glass (X=0)
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40 and co-precursor (X=2), N2 adsorption desorption isotherm and pore size distribution are represented in
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43 Figure1 (d) and (e). The typical IV type isotherms and the hysteresis loops of aerogels indicated that there
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46 are abundant mesopores in the material [20]. The SiO2 aerogel showed an ink-bottle shaped pore [21] with
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49 the H4 hysteresis loops, while PMSQ aerogel showed a muddy pore [22] with the H3 hysteresis loop. The
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average pore size distribution of SiO2 aerogels was 40 Å, while PMSQ aerogels showed a larger pore size
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54 distribution of 110 Å. In more detail, the high specific surface area of 389 m2 g-1 and 565 m2 g-1 (shown in
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2 Tab.1) was also measured, which further indicated that the porous structure of silica aerogel network
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5 remained in composites after the introduction of the fibers.
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7 Another important factor affecting the pore size distribution of composites is the number of Si-CH3 groups
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10 on the surface, which was determined by MTMS. Table 1 lists a summary of pore size distribution with
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13 different X. It was obvious that the specific surface area first increased and then decreased with the
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16 increasing of X, noting that a further increase of X in composite would result in a remarkable reduction in
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18 surface area, which was assumed to be the result of agglomeration of organic particles in the gel network
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21 [23]. Besides, the pore size distribution for X=1.0 was similar to that of X=0, while it became wider and
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24 the peak value decreased with the further increase of X (shown in Figure 2(f)). Accordingly, in the N2
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27 adsorption-desorption isotherm curve, the samples with low X value (X=1.0) showed the same H4
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29 hysteresis loop as the samples prepared by pure water glass, while the samples show H3 hysteresis loop
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32 with the further increase of X (shown in Figure 2(e)).
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35 Adjusting the volume of silica sol and the molar ratio of MTMS/water glass can readily turn the physical
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38 properties of aerogel composites. Figure 2(a) and (b) shows the microstructure of the composite with the
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40 increasing silica sol and molar ratio of co- precursors. It showed that the number of silica nanoparticles
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43 growing on the fiber surface increased with the increase of silica sol, which was also reflected in the bulk
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46 density of the composite. When the molar ratio of the co-precursor was set to 2.0, the bulk density of the
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49 composites first increased and then decreased to 0.1768 g cm-3 with the silica sol increased from 0.75 to
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3.0 ml. The porosity showed the opposite trend, and increased to 79.29 % at the volume of 3.0 ml (shown
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54 in Figure 2(c)). However, the increased volume and limited weight growth of composite led to the decrease
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57 of the bulk density at the volume of 3.0 ml. When the volume of silica sol was set to 3.0 ml, the bulk density
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2 first decreased to 0.1615 g cm-3 and then grew up with the molar ratio increased from 0 to 2.9. The porosity
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5 showed an opposite trend and reached the maximum value of 81.12% at a molar ratio of 1.0 (shown in
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7 Figure 2(d)). This could be attributed to the accumulation of particles, which shown in Figure 2(b) [24].
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11 3.2. Thermal Protection Performance of the AF-HSiO2 composites
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15 Benefiting from the high porosity and low thermal conductivity characteristics of silica aerogels, the as-
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18 prepared AF-HSiO2 aerogel composites hold great thermal protection performance [23]. Figure 3 illustrated
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21 the excellent thermal protection performance (TPP) of the composite with the increase of silica sol, in which
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23 the TPP value and second-degree burn time reached the maximum values of 12.16 cal cm-2 and 6.23 s at
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26 the volume of 3 ml, respectively. This result could also be observed in Figure 3(e) and (f), i.e., the
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29 temperature of composites gradually slowed down during the thermal exposure period with the increase of
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32 silica sol, resulting in the increase of the temperature difference between the composite and pure AF. In
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addition, due to the increase of flame retardancy caused by the increase of Si-CH3 groups in the composites
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37 [25], the temperature difference decreased slightly at the volume of 3 ml (Figure 3(f)).
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40 Generally, the thermal conductivity of aerogels at room temperature is mainly caused by conduction,
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43 convection and radiation [26], while the thermal conductivity at high temperature is affected by the heat
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transfer of solid phase (λs) and gas phase (λg). The heat transfer of solid phase (λs) could be reduced by
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48 decreasing the bulk density of aerogels, while the heat transfer in gas phase (λg) could be achieved by
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51 increasing the mesoporous and narrowing the pore size. Therefore, the TPP value and second-degree burn
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54 time increased suddenly to 11.363 cal cm-2 and 5.816 s at the molar ratio 1.0, respectively, which was also
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shown in the temperature-time curve and the temperature difference with the sample prepared by pure water
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59 glass (Figure3 (h) and (i)). Besides, the decomposition temperature of composites was about 450 °C in
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2 nitrogen (Figure3 (c)), and the oxidative decomposition of Si-CH3 groups in PMSQ at high temperature led
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5 to greater weight loss than that of AF-SiO2 composites. Although the presence of AF fibers limited the
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7 durable temperature, AF-HSiO2 aerogel composites still attracted attention as thermal protection materials
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10 for practical applications.
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14 3.3. Mechanical and Hydrophobicity Properties of the AF-HSiO2 aerogel composites
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18 The SEM picture in Figure 4(c) shows the disordered and randomly distributed fibers in AF nonwovens.
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21 They tangled the layers to form a tightly wound and porous anisotropic 3D fiber structure rather than a
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23 simple fiber stacking. The synergistic combination of anisotropic AF fiber matrix and porous SiO2 or PMSQ
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26 network can effectively enhance the mechanical properties of composites. All composites exhibited
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29 exceptionally high tensile strength (237.1-319.2 N) and elongation (45.22-51.19 %) (shown in Figure4).
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32 This observation was unexpected due to the difference from the conventional and high porosity silica
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aerogels (>88%) which were typically fragile [2]. This significant strength enhancement could be due to
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37 the physical support of AF nonwovens and the elasticity of Si-CH3 groups [27], which together provide
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40 excellent mechanical properties of composites. However, with the further increase of molar ratio, the
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43 formation of clusters and macropores in the gel network of PMSQ and the accumulation of particles led to
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a weak gel skeleton structure, which eventually reduced the strength of the composites to 237.1N.
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48 AF-SiO2 composites showed hydrophilicity with contact angle of 0° due to the surface hydrophilicity of
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51 SiO2 network, while AF-PMSQ composites exhibited hydrophobicity with the contact angle of 136° due to
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54 the surface hydrophobicity of PMSQ network (shown in Figure 4). As shown in illustration, the hydroxyl
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groups connected to the silicon atoms contributed to the formation of hydrophilic surfaces of composites,
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59 while the corresponding methyl groups were mainly contributed to the hydrophobic surfaces of the
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2 composites. Besides, the contact angle of the AF-PMSQ composites increased with the increase of molar
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5 ratio, which was related to the increased amount of methyl groups on the material surface [17]. Thus, the
6
7 composites gradually changed from hydrophilicity to hydrophobicity.
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9
10 4. Conclusions
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12
13 We reported an eco-friendly method to prepare a novel AF-HSiO2 aerogel composite by combining
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16 aramid nonwovens and hybrid silica aerogels followed by the freeze-drying method. The microstructure,
17
18 thermal protection performance and mechanical properties of the composites with different volume of silica
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21 sol and molar ratio of MTMS to water glass (0-2.9) were systematically measured and analyzed.
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24 Benefiting from the excellent structural characteristics, e.g., the low density (0.1615 m3 g-1), high
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27 porosity (81.12 %) and high specific surface area (659 m2 g-1), the obtained composites showed high
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29 thermal protection performance with a TPP value of 11.36 cal cm-2 and second degree burn time of 5.82 s
30
31
32 as well as high tensile strength (319.2 N). Additionally, the resultant AF-PMSQ composites exhibited
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35 intrinsic hydrophobicity performance, due to the abundant methyl groups on the surface of PMSQ, thus it
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38 could be used in high temperature and high humid environment. These outstanding characteristics indicated
39
40 that the obtained AF-HSiO2 aerogel composites can be widely used in the field of thermal protection.
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42
43 Acknowledgment
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46 This study was supported by the Nation Key R&D Program of China (2017YFB0309100), China
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48
49 Postdoctoral Science Foundation (No.2019T120390); Jiangsu Planned Projects for Postdoctoral research
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funds (No. 2018K018A) ；the National Natural Science Foundation of China [No.31470509] and the Key
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54 Laboratory of Eco-textiles, Ministry of Education— (supported by “the Fundamental Research Funds for
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57 the Central Universities NO. JUSRP52007A).
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46 Statements and Declarations
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49 Conflict of interest：The authors declare that they have no conflict of interest.
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Tables
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54 Table 1. Pore parameters of different samples
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56 X BET surface area(m2/g) Pore volume (cm3/g) Average pore size(nm)
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 1 0 388.538 0.414 3.870
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3 1.0 659.002 0.840 7.697
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5 1.5 628.833 0.856 7.108
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7 2.0 564.976 0.679 9.433
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9 2.9 398.074 0.391 4.748
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12 Figure Captions
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41 Figure 1. Preparation process, macro- and microscopic structure of the AF-HSiO2 aerogel composite.
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44 (a) Experimental procedure for the synthesis of AF-HSiO2 aerogel composite. (b) SEM of AF, AF-SiO2
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47 and AF-PMSQ aerogel composite. (c) FTIR spectrum of AF, AF/SiO 2 and AF/PMSQ aerogel composite.
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(d) N2 adsorption-desorption isotherms and (e) Pore size distribution of AF, AF/SiO2 and AF/PMSQ
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52 aerogel composite.
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21 Figure 2. (a) and (b) AF-HSiO2 aerogel composites with different silica sol of 0, 0.75, 1.8, 2.5 and 3.0;
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24 and different molar ratio of X=1.0, X=1.5, X= 2.0, X= 2.9. (c) and (d) Bulk density and porosity of
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27 composites with different volume of silica sol and molar ratios of co-precursors. (e) N2 adsorption-
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29 desorption isotherms and (f) Pore size distribution of composites prepared with various molar ratio.
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2 Figure 3. Thermal protection performance of AF-HSiO2 aerogel composite under the high heat flux of
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5 84±2 kW/m2. (a) and (b) photography of the TPP instrument and its structure diagram. (c) The TG curves
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7 of AF, AF-SiO2 and AF-PMSQ composites. (d) The TPP values and second-degree burn times and (e)
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10 Time-temperature curves and (f) Time-temperature difference of composites with increasing silica sol (Ti
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13 is the temperature of composites; T AF is the temperature of AF). (g-i) the same as (d-f) but with different
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16 molar ratio of MTMS/water glass (T X=0 is the temperature of X=0).
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36 Figure 4. The tensile strength and photograph of the contact angle of AF-HSiO2 aerogel composites with
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39 the increasing molar ratio. (a) and (b) Schematic diagram of aramid fiber fabric covered with -CH3 and -
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42 OH groups. (c) SEM of aramid fiber fabric with intertwined internal fibers. (d) The tensile strength and
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elongation of composites with increasing X. (e) photograph of the contact angle of composites with
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47 increasing X.
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50 Appendix A.
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53 Porosity = ((1/ρb) − (1/ρs) − (1/ρf)) × 100% /(1/ρb)
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56 Appendix B.
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