无机酸铝体系氧化铝连续纤维的制备技术研究

doi:10.15541/jim20230153

无机材料学报 ›› 2023, Vol. 38 ›› Issue (11): 1257-1264.DOI: 10.15541/jim20230153

所属专题：【结构材料】超高温结构陶瓷(202312)

无机酸铝体系氧化铝连续纤维的制备技术研究

贾玉娜¹(), 曹旭², 焦秀玲¹, 陈代荣¹()

1.山东大学国家胶体材料工程技术研究中心, 济南250100
2.北京空间机电研究所, 北京100076

收稿日期:2023-03-27 修回日期:2023-05-19 出版日期:2023-05-22 网络出版日期:2023-05-22
通讯作者: 陈代荣, 教授. E-mail: cdr@sdu.edu.cn
作者简介:贾玉娜 (1976-), 女, 高级工程师. E-mail: jiayuna@sdu.edu.cn
基金资助:
中国航天科技航天进入减速与着陆技术实验室开放基金(EDL9092122)

Preparation of Alumina Ceramic Continuous Fibers with Inorganic Acidic Aluminum Sol as Precursor

JIA Yuna¹(), CAO Xu², JIAO Xiuling¹, CHEN Dairong¹()

1. National Engineering Research Center for Colloidal Materials, Shandong University, Jinan 250100, China
2. Beijing Institute of Space Mechanics & Electricity, Beijing 100076, China

Received:2023-03-27 Revised:2023-05-19 Published:2023-05-22 Online:2023-05-22
Contact: CHEN Dairong, professor. E-mail: cdr@sdu.edu.cn
About author:JIA Yuna (1976-), female, senior engineer. E-mail: jiayuna@sdu.edu.cn
Supported by:
Fund of Laboratory of Aerospace Entry, Descent and Landing Technology(EDL9092122)

摘要/Abstract

摘要：

作为一种性能优异的耐高温结构增强材料, 氧化铝连续纤维应用广泛, 但其规模化制备流程长, 技术难度大。本研究以自制的铝溶胶和市售硅溶胶为前驱体, 研究了铝溶胶的微观结构和组成, 探讨了溶胶具有优异可纺性的原因。通过溶胶-凝胶结合干法纺丝技术制备了氧化铝基凝胶连续纤维, 纤维长度可达1500 m以上, 进一步高温陶瓷化后形成了直径约为10 μm、主晶相为γ-Al₂O₃和无定型SiO₂的氧化铝陶瓷连续纤维, 其中在1100 ℃下煅烧30 min所制备的纤维单丝平均拉伸强度达到2.0 GPa。微观结构分析表明陶瓷纤维结构致密, 其中粒度仅为10~ 20 nm的γ-Al₂O₃晶粒均匀分布于无定型SiO₂中, 使纤维表现出优异的力学性能。该制备过程绿色简单可控, 具有产业化应用前景。进一步对氧化铝连续纤维的耐高温性能进行了分析, 结果表明氧化铝连续纤维可在1000 ℃长时间使用, 短时使用温度可达1300 ℃。

关键词: 氧化铝连续纤维, 溶胶-凝胶法, 铝溶胶, 干法纺丝

Abstract:

As a high-temperature-resistant structural reinforcement material with excellent performance, alumina continuous fiber has been widely used in various fields. However, its large-scale preparation is still a great challenge due to the technical difficulty. Herein, the alumina continuous fibers were prepared using self-made aluminum sol and commercially available silica sol as precursors, in which the microstructure and composition of aluminum sol were studied to reveal their excellent spinnability. Preparation of alumina-based gel continuous fibers with length longer than 1500 m was realized by Sol-Gel combined dry spinning technology. After calcination at 1100 ℃ for 30 min, the continuous ceramic fiber composed of γ-Al₂O₃ and amorphous SiO₂ with the diameter and mean tensile strength of 10 μm and 2.0 GPa was successfully obtained. Microstructure analyses revealed high relative density of the ceramic fibers, in which the γ-Al₂O₃ nanocrystals with size of 10-20 nm uniformly distributed in amorphous SiO₂, resulting in excellent mechanical properties. This preparation process is environment-friendly, simple and controllable, showing great potential in practical application. The test for high temperature resistance revealed that the alumina continuous fiber can work for a long time at 1000 ℃ while it can endure as high as 1300 ℃ for a short-time service.

Key words: alumina continuous ceramic fibers, Sol-Gel technology, aluminum sol, dry spinning

中图分类号:

TB321

贾玉娜, 曹旭, 焦秀玲, 陈代荣. 无机酸铝体系氧化铝连续纤维的制备技术研究[J]. 无机材料学报, 2023, 38(11): 1257-1264.

JIA Yuna, CAO Xu, JIAO Xiuling, CHEN Dairong. Preparation of Alumina Ceramic Continuous Fibers with Inorganic Acidic Aluminum Sol as Precursor[J]. Journal of Inorganic Materials, 2023, 38(11): 1257-1264.

图/表 11

图1 不同n(Al(OH)3)∶n(AlCl3)的铝溶胶的27Al核磁谱(a)和n(Al(OH)3)∶n(AlCl3)=1:0.35时, 复合溶胶的粒径分布曲线(b)

Fig. 1 (a) 27Al NMR spectra of aluminum sol prepared with different n(Al(OH)3)∶n(AlCl3) and (b) particle size distributions of hybrid sol with n(Al(OH)3)∶n(AlCl3) at 1:0.35

图2 溶胶的流变曲线

Fig. 2 Rheological curves of sol (a) Apparent viscosities of the sol with different solid contents as a function of shear rate, and (b) relationship between apparent viscosity of spinnable sol and temperature

图3 凝胶纤维的扫描电镜照片

Fig. 3 SEM images of the gel fibers (a) Overview; (b) Fiber’s surface

图4 凝胶纤维的红外谱图(a)、热分析(TG-DSC)曲线(b)和不同温度煅烧后纤维的XRD图谱(c)

Fig. 4 FT-IR spectra (a), TG-DSC curves (b) of the gel fibers, and (c) XRD patterns of the fibers calcined at different temperatures

图5 不同温度煅烧后的纤维全貌、表面和截面的SEM照片

Fig. 5 SEM images of surfaces and cross sections of the fibers calcined at different temperatures

表1 不同煅烧温度所制备纤维的密度及强度

Table 1 Densities and strengths of fibers calcined at different temperatures

Calcination conditions	Tensile strength/GPa	Cv of tensile strength/%	Density/(g·cm^-3)	Crystalline size/nm	Phase composition
900 ℃/30 min	1.5	12.33	2.86	9.80	γ-Al₂O₃ + amorphous
1000 ℃/30 min	1.6	11.26	2.91	10.36	γ-Al₂O₃ + amorphous
1100 ℃/30 min	2.0	12.68	2.95	10.77	γ-Al₂O₃ + amorphous
1200 ℃/30 min	1.4	12.17	2.85	11.63	γ-Al₂O₃ + amorphous

图6 氧化铝陶瓷连续纤维的TEM(a)和高分辨TEM(b)照片

Fig. 6 TEM (a) and high resolution TEM (b) images of alumina ceramic continuous fiber with insets in (a) showing low magnification image and SAED pattern of the fiber

图7 不同条件热处理后氧化铝连续纤维的XRD图谱

Fig. 7 XRD patterns of alumina continuous fibers after heat-treatment under different conditions

表2 不同条件热处理后氧化铝连续纤维的力学性能

Table 2 Mechanical properties of alumina continuous fibers after heat treatment under different conditions

Calcination conditions	Shrinkage ratio of diameter/%	Tensile strength/GPa	Cv of tensile strength/%	Retention rate/%	Phase composition
Original fiber	—	2.035	13.70	—	γ-Al₂O₃ + amorphous
1000 ℃/1 h	0	2.002	12.89	98.38	γ-Al₂O₃ + amorphous
1100 ℃/1 h	0	1.933	13.01	94.99	γ-Al₂O₃ + amorphous
1200 ℃/1 h	0.82	1.842	14.02	90.52	γ-Al₂O₃ + amorphous
1300 ℃/0.5 h	1.95	1.579	14.57	77.59	Mullite +γ-Al₂O₃ + amorphous
1400 ℃/0.5 h	2.36	0.419	15.03	20.59	Mullite
1000 ℃/20 h	0.28	1.926	13.24	94.64	γ-Al₂O₃ + amorphous
1000 ℃/40 h	1.66	1.857	13.95	91.25	γ-Al₂O₃ + amorphous

图S1 氧化铝陶瓷连续纤维经不同温度热处理后的SEM照片(全貌(1)、表面(2)、截面(3))

Fig. S1 SEM images of alumina ceramic continuous fiber after heat-treatment at different temperatures (overview (a1-e1), surface (a2-e2), cross section (a3-e3)) (a) 1000 ℃/1 h; (b) 1100 ℃/1 h; (c) 1200 ℃/1 h; (d) 1300 ℃/0.5 h; (e) 1400 ℃/0.5 h

图S2 1000 ℃不同保温时间的氧化铝陶瓷连续纤维的SEM照片(全貌(1)、表面(2)、截面(3))

Fig. S2 SEM images of alumina ceramic continuous fiber at 1000 ℃ with different holding time (overview (a1-b1), surface (a2-b2), cross section (a3-b3)) (a) 1000 ℃/20 h; (b) 1000 ℃/40 h

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无机酸铝体系氧化铝连续纤维的制备技术研究

Preparation of Alumina Ceramic Continuous Fibers with Inorganic Acidic Aluminum Sol as Precursor

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