磷钼酸插层水滑石复合CNFs气凝胶的制备及其隔热保温性能

doi:10.15541/jim20240378

无机材料学报 ›› 2025, Vol. 40 ›› Issue (4): 415-424.DOI: 10.15541/jim20240378 CSTR: 32189.14.10.15541/jim20240378

磷钼酸插层水滑石复合CNFs气凝胶的制备及其隔热保温性能

袁利萍¹(), 吴袁泊¹, 俞佳静¹, 张世琰¹, 孙铱¹, 胡云楚¹, 范友华²()

1.中南林业科技大学材料科学与工程学院, 长沙 410004
2.湖南省林业科学院, 长沙 410018

收稿日期:2024-08-15 修回日期:2024-12-16 出版日期:2024-12-27 网络出版日期:2024-12-27
通讯作者: 范友华, 研究员. E-mail: yh_fan@163.com
作者简介:袁利萍(1975-), 女, 副教授. E-mail: tiansiyuan@126.com
基金资助:
湖南省教育厅科学研究项目(23A0202);长沙市自然科学基金项目(2022kq100);中央财政林业科技推广示范资金项目([2022] XT02)

CNFs Aerogel Composite with Phosphomolybdic Acid Intercalated Hydrotalcite: Preparation and Thermal Insulation Performance

YUAN Liping¹(), WU Yuanbo¹, YU Jiajing¹, ZHANG Shiyan¹, SUN Yi¹, HU Yunchu¹, FAN Youhua²()

1. School of Material Science and Engineering, Central South University of Forestry and Technology, Changsha 410004, China
2. Hunan Academy of Forestry, Changsha 410018, China

Received:2024-08-15 Revised:2024-12-16 Published:2024-12-27 Online:2024-12-27
Contact: FAN Youhua, professor. E-mail: yh_fan@163.com
About author:YUAN Liping (1975-), female, associate professor. E-mail: tiansiyuan@126.com
Supported by:
Scientific Research Project of Hunan Provincial Department of Education(23A0202);Changsha Natural Science Foundation Project(2022kq100);Central Finance Forestry Science and Technology Promotion Demonstration Fund Project([2022] XT02)

摘要/Abstract

摘要：

轻质、隔热和耐高温材料是航天人员和精密设备的必要保障。纳米纤维素(CNFs)因高比表面积、低热膨胀系数和高强度等特性, 在轻质航天航空材料领域具有潜在的应用前景, 但是质脆易燃限制了其在高温领域的广泛应用。为了提升CNFs的耐高温性能, 本工作采用共沉淀法和离子交换法成功制备了[PMo₁₂O₄₀]^3-插层改性的ZnAl-PMo₁₂O₄₀-LDHs(PMo-LDHs, LDHs: 类水滑石插层材料), 将其与硼酸(BA)复合CNFs制备了PMo-LDHs+BA/CNFs气凝胶。当PMo-LDHs和BA的质量分数分别为CNFs的62.5%和2.0%时, 所制得的62.5PMo-LDHs+BA/CNFs气凝胶的密度为16.28 kg·m^-3, 导热系数为0.044 W/(m·K)。隔热背温实验表明, 该气凝胶的t₂₅₀(隔热背温达到250 ℃所需时间)长达2022.8 s, 比纯CNFs延长867.8 s; 其R₂₅₀(隔热背温达到250 ℃时的升温速率)只有0.124 ℃·s^-1, 仅为纯CNFs R₂₅₀的57.4%, 表现出优异的隔热保温性能。灼烧实验显示, 纯CNFs气凝胶在15 s内完全燃烧, 而62.5PMo-LDHs+BA/CNFs气凝胶在81 s内未被点燃, 且未出现明显收缩或变形。燃烧残余物的形貌结果表明, PMo-LDHs受热分解, 在CNFs基材表面催化形成致密均匀的连续炭层, 从而提高了CNFs气凝胶的耐火性能。

关键词: 磷钼酸, 插层水滑石, 纳米纤维素, 气凝胶, 隔热保温

Abstract:

Light-weight, heat-insulating and high-temperature resistant materials are essential for safety of astronauts and precision equipments. Nanocellulose (CNFs), with high specific surface area, low thermal expansion coefficient and high strength, has application prospects in preparation of light-weight and thermal insulation aviation materials. However, brittleness and high flammability of CNFs limit their widespread use in high-temperature fields. In order to improve the high temperature resistance of CNFs, [PMo₁₂O₄₀]^3- intercalated ZnAl-PMo₁₂O₄₀-LDHs (PMo-LDHs, LDHs: layered double hydroxides) were successfully synthesized by co-precipitation and ion-exchange methods. Then the PMo-LDHs+BA/CNFs aerogel was prepared by combining ZnAl-PMo₁₂O₄₀-LDHs with boric acid (BA) to formulate CNFs composites. When the mass fractions of PMo-LDHs and BA are 62.5% and 2.0% of CNFs, density and thermal conductivity of 62.5PMo-LDHs+BA/CNFs aerogel are 16.28 kg·m^-3 and 0.044 W/(m·K), respectively. Thermal insulation back-fire temperature experiments indicate that t₂₅₀(time required to reach a thermal insulation temperature of 250 ℃) of 62.5PMo-LDHs+BA/CNFs aerogel is 2022.8 s, which is 867.8 s longer than that of pure CNFs aerogel. R₂₅₀(heating rate when an insulation temperature reaches 250 ℃) is only 0.124 ℃·s^-1, which is 57.4% of R₂₅₀ for pure CNFs aerogel, demonstrating an exceptionally excellent thermal insulation effect. Combustion experiments reveal that the pure CNFs aerogel undergoes complete combustion within 15 s, whereas 62.5PMo-LDHs+BA/CNFs aerogel does not ignite within 81 s and exhibits no obvious shrinkage or deformation. Morphological observation of combustion residues indicates that a dense and uniform continuous carbon layer is formed on the surface of the aerogel due to the decomposition of PMo-LDHs, which significantly improves fire resistance of the CNFs aerogel.

Key words: phosphomolybdic acid, intercalated hydrotalcite, nanocellulose, aerogel, thermal insulation

中图分类号:

TQ352

袁利萍, 吴袁泊, 俞佳静, 张世琰, 孙铱, 胡云楚, 范友华. 磷钼酸插层水滑石复合CNFs气凝胶的制备及其隔热保温性能[J]. 无机材料学报, 2025, 40(4): 415-424.

YUAN Liping, WU Yuanbo, YU Jiajing, ZHANG Shiyan, SUN Yi, HU Yunchu, FAN Youhua. CNFs Aerogel Composite with Phosphomolybdic Acid Intercalated Hydrotalcite: Preparation and Thermal Insulation Performance[J]. Journal of Inorganic Materials, 2025, 40(4): 415-424.

图/表 14

表1 LDHs/CNFs气凝胶的组成配方和密度

Table 1 Composition formula and density of LDHs/CNFs aerogel

No.	Sample	CNFs/mL	NO₃-LDHs/g	PMo-LDHs/g	BA/g	ρ/(kg·m^-3)
1	CNFs	10.0	—	—	—	10.01
2	NO₃-LDHs/CNFs	10.0	0.0375	—	—	14.12
3	PMo-LDHs/CNFs	10.0	—	0.0375	—	14.23
4	NO₃-LDHs+BA/CNFs	10.0	0.0375	—	0.0020	14.67
5	PMo-LDHs+BA/CNFs	10.0	—	0.0375	0.0020	14.95
6	50.0PMo-LDHs+BA/CNFs	10.0	—	0.0500	0.0020	15.72
7	62.5PMo-LDHs+BA/CNFs	10.0	—	0.0625	0.0020	16.28

图1 隔热背温实验装置示意图

Fig. 1 Schematic diagram of thermal insulation back-fire temperature experiment

图2 NO3-LDHs与PMo-LDHs的XRD图谱

Fig. 2 XRD patterns of NO3-LDHs and PMo-LDHs

表2 NO3-LDHs与PMo-LDHs的晶面间距和晶格参数

Table 2 Interplanar spacing and lattice parameters of NO3-LDHs and PMo-LDHs

Sample	d₍₀₀₃₎/nm	d₍₀₀₆₎/nm	d₍₀₀₉₎/nm	d₍₁₁₀₎/nm	2θ₍₀₀₃₎/(^o)	a/nm	c/nm
NO₃-LDHs	0.888	0.445	0.265	0.153	9.94	0.307	2.67
PMo-LDHs	0.975	0.488	0.267	0.153	9.06	0.306	2.92

图3 (a) NO3-LDHs和(b) PMo-LDHs的SEM照片

Fig. 3 SEM images of (a) NO3-LDHs and (b) PMo-LDHs

图4 62.5PMo-LDHs+BA/CNFs气凝胶的(a)外观形貌及其置于(b)砝码下和(c)花瓣上的照片

Fig. 4 Morphology of 62.5PMo-LDHs+BA/CNFs aerogel (a) and digital photos when it placed (b) under weight and (c) on petals

图5 (a, a')纯CNFs、(b, b')NO3-LDHs+BA/CNFs和(c, c') 62.5PMo-LDHs+BA/CNFs气凝胶的SEM照片

Fig. 5 SEM images of (a, a') pure CNFs, (b, b') NO3-LDHs+BA/CNFs, and (c, c') 62.5PMo-LDHs+BA/CNFs aerogels

图6 LDHs/CNFs气凝胶的FT-IR图谱

Fig. 6 FT-IR spectra of LDHs/CNFs aerogels

图7 LDHs/CNFs气凝胶的(a) TG和(b) DTG曲线

Fig. 7 (a) TG and (b) DTG curves of LDHs/CNFs aerogels Colorful figures are available on website

表3 LDHs/CNFs气凝胶的TG/DTG参数

Table 3 TG/DTG parameters of LDHs/CNFs aerogels

Sample	T₁/℃	R₁/(%·℃^-1)	T₂/℃	R₂/(%·℃^-1)	T₅₀/℃	M₈₀₀/%
CNFs	56.7	0.186	257.3	0.569	297.1	20.8
NO₃-LDHs/CNFs	58.1	0.160	304.5	0.595	322.7	23.6
PMo-LDHs/CNFs	55.7	0.172	286.8	0.418	360.1	27.3
NO₃-LDHs+BA/CNFs	48.2	0.157	305.6	0.587	348.7	27.2
PMo-LDHs+BA/CNFs	53.5	0.169	295.8	0.401	381.2	27.6
50.0PMo-LDHs+BA/CNFs	51.8	0.154	294.1	0.352	423.4	31.9
62.5PMo-LDHs+BA/CNFs	50.7	0.127	282.2	0.306	620.2	38.9

图8 LDHs/CNFs气凝胶的(a)隔热背温曲线和(b) 750 s后隔热背温曲线放大图

Fig. 8 Thermal insulation back-fire temperature curves (a) and magnified curves of thermal insulation back-fire temperature curves after 750 s (b) of LDHs/CNFs aerogels Colorful figures are available on website

表4 LDHs/CNFs气凝胶的隔热背温参数和导热系数

Table 4 Thermal insulation back-fire temperature test parameters and thermal conductivity of LDHs/CNFs aerogels

Sample	t₂₀₀/s	t₂₅₀/s	R₂₀₀/(℃·s^-1)	R₂₅₀/(℃·s^-1)	λ/(W·m^-1·K^-1)
CNFs	685.4	1155.0	0.292	0.216	0.045
NO₃-LDHs/CNFs	739.4	1306.6	0.270	0.191	—
PMo-LDHs/CNFs	776.7	1527.5	0.258	0.164	—
NO₃-LDHs+BA/CNFs	793.5	1524.4	0.252	0.164	0.047
PMo-LDHs+BA/CNFs	837.6	1642.6	0.239	0.152	—
50.0PMo-LDHs+BA/CNFs	857.6	1771.2	0.233	0.141	—
62.5PMo-LDHs+BA/CNFs	886.5	2022.8	0.226	0.124	0.044

图9 (a)纯CNFs、(b) NO3-LDHs+BA/CNFs和(c) 62.5PMo-LDHs+BA/CNFs气凝胶的灼烧试验

Fig. 9 Combustion tests of (a) pure CNFs, (b) NO3-LDHs+BA/CNFs, and (c) 62.5PMo-LDHs+BA/CNFs aerogels

图10 (a)纯CNFs、(b) NO3-LDHs+BA/CNFs和(c) 62.5PMo-LDHs+BA/CNFs气凝胶灼烧残余物的SEM照片

Fig. 10 SEM images of combustion residues of (a) pure CNFs, (b) NO3-LDHs+BA/CNFs, and (c) 62.5PMo-LDHs+BA/CNFs aerogels

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磷钼酸插层水滑石复合CNFs气凝胶的制备及其隔热保温性能

CNFs Aerogel Composite with Phosphomolybdic Acid Intercalated Hydrotalcite: Preparation and Thermal Insulation Performance

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