吸附-沉淀自组装结合放电等离子烧结法制备石墨烯增强氧化铝复合陶瓷

doi:10.15541/jim20250140

无机材料学报 ›› 2026, Vol. 41 ›› Issue (4): 536-544.DOI: 10.15541/jim20250140 CSTR: 32189.14.jim20250140

• 研究快报 • 上一篇

吸附-沉淀自组装结合放电等离子烧结法制备石墨烯增强氧化铝复合陶瓷

程澳芃¹^,²^,³(), 王跃文²^,³^,⁴, 许文涛²^,⁵^,⁶(), 刘全伟²^,³^,⁴, 张海涛²^,⁵^,⁶, 周有福²^,⁵^,⁶

¹ 福州大学化学学院, 福州 350108
² 中国科学院福建物质结构研究所, 功能晶体与器件全国重点实验室, 福州 350002
³ 中国科学院大学福建学院, 福州 350002
⁴ 福建师范大学化学与材料科学学院, 福州 350002
⁵ 中国科学院福建物质结构研究所, 光电材料化学与物理重点实验室, 福州 350002
⁶ 福建光电信息科技创新实验室, 福州 350108

收稿日期:2025-04-04 修回日期:2025-06-06 出版日期:2025-06-10 网络出版日期:2025-06-10
通讯作者: 许文涛, 副研究员. E-mail: wtxu@fjirsm.ac.cn
作者简介:程澳芃(1999-), 男, 硕士研究生. E-mail: chengaopeng@fjirsm.ac.cn

Fabrication of Graphene-reinforced Alumina Ceramic Composites via Adsorption-precipitation Self-assembly Combined with Spark Plasma Sintering

CHENG Aopeng¹^,²^,³(), WANG Yuewen²^,³^,⁴, XU Wentao²^,⁵^,⁶(), LIU Quanwei²^,³^,⁴, ZHANG Haitao²^,⁵^,⁶, ZHOU Youfu²^,⁵^,⁶

¹ College of Chemistry, Fuzhou University, Fuzhou 350108, China
² State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Mater, Chinese Academy of Sciences, Fuzhou 350002, China
³ Fujian College, University of Chinese Academy of Sciences, Fuzhou 350002, China
⁴ College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350002, China
⁵ Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Mater, Chinese Academy of Sciences, Fuzhou 350002, China
⁶ Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China

Received:2025-04-04 Revised:2025-06-06 Published:2025-06-10 Online:2025-06-10
Contact: XU Wentao, associate professor. E-mail: wtxu@fjirsm.ac.cn
About author:CHENG Aopeng (1999-), male, Master candidate. E-mail: chengaopeng@fjirsm.ac.cn
Supported by:
National Key Research and Development Program of China(2022YFB3708500);National Key Research and Development Program of China(2023YFB3611000);Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(2020ZZ109);Natural Science Foundation of Fujian Province(2025H0035)

摘要/Abstract

摘要：

氧化铝陶瓷是广泛应用的结构材料, 但固有脆性和单一功能限制了其在高性能要求环境中的应用。二维石墨烯具有优异的机械、热和电特性, 将其组装入陶瓷基体, 可通过界面工程促进晶粒细化, 实现性能优化。传统的物理混合方法导致石墨烯片的均匀性和完整性较差, 阻碍了复合材料的发展。针对上述问题, 本工作提出了一种新型的吸附沉淀自组装(APSA)方法, 能够实现氧化石墨烯(GO)薄片与亚微米Al₂O₃颗粒无损复合。通过在GO表面吸附Al³⁺离子实现均匀沉积, 可获得均匀前驱体, 进一步结合放电等离子烧结(SPS)可实现低温快速致密化。在制备的复合陶瓷中, 石墨烯沿着氧化铝晶粒平行排列, 促进了晶粒细化, 并通过拉出、裂纹扩展和桥接等多种增韧机制的协同作用显著提高了材料的机械性能。与单一氧化铝陶瓷相比, 复合陶瓷的抗弯强度((428±87) MPa)提高了43%, 断裂韧性((4.40±0.13) MPa·m^1/2)提高了34%。此外, 与传统球磨混合工艺制备的试样相比, 强度和韧性也分别提高了15%, 进一步证实该技术路线的有效性与先进性。

关键词: 石墨烯, 氧化铝, 复合陶瓷, 强韧化, 自组装

Abstract:

Alumina ceramics are widely utilized as structural materials, yet their inherent brittleness and monofunctionality limit their application in high-stress scenarios. Strategic integration of two-dimensional graphene sheets, characterized by their excellent mechanical, thermal and electrical properties, into ceramic matrix can facilitate grain refinement through interface engineering, thereby achieving performance optimization. Conventional physical blending methods result in poor uniformity and integrity of 2D sheets, thereby impeding advancements in graphene-ceramic composites. Herein, a novel adsorption-precipitation self-assembly (APSA) method was proposed for the nondestructive integration of graphene oxide (GO) sheets with submicron Al₂O₃ particles. A homogeneous precursor is obtained by uniform deposition of Al³⁺ ions adsorbed on GO surface, followed by low-temperature rapid densification via spark plasma sintering (SPS). For the resultant composites, the incorporated graphene is aligned parallel to the alumina grains, facilitating grain refinement and significantly enhancing the mechanical properties through synergistic effect of various toughening mechanisms, including pull-out, crack extension and bridging. In comparison to monolithic alumina ceramics, the ceramic composites exhibit a 43% enhancement in flexural strength ((428±87) MPa) and a 34% improvement in fracture toughness ((4.40±0.13) MPa·m^1/2). Furthermore, the strength and toughness values also increase by 15% respectively, compared to specimens made from the conventional ball-milling mixing process, confirming the efficacy and advancement of such a manufacturing approach.

Key words: graphene, alumina, ceramic composite, reinforcement, self-assembly

中图分类号:

TQ174

程澳芃, 王跃文, 许文涛, 刘全伟, 张海涛, 周有福. 吸附-沉淀自组装结合放电等离子烧结法制备石墨烯增强氧化铝复合陶瓷[J]. 无机材料学报, 2026, 41(4): 536-544.

CHENG Aopeng, WANG Yuewen, XU Wentao, LIU Quanwei, ZHANG Haitao, ZHOU Youfu. Fabrication of Graphene-reinforced Alumina Ceramic Composites via Adsorption-precipitation Self-assembly Combined with Spark Plasma Sintering[J]. Journal of Inorganic Materials, 2026, 41(4): 536-544.

图/表 14

Fig. 1 Schematic illustration of preparing process for hybrid precursors by APSA method

Fig. 2 (a) Zeta potential of GO dispersion as a function of pH with inset showing the Zeta potentials for different Al3+ ions added to the GO solution; (b) XRD patterns of the precursors before and after calcination; (c, d) SEM images of 5rGO-Al2O3 precursor (c) before and (d) after calcinations

Fig. 3 Fracture surface morphologies of the SPSed ceramics (a) Monolithic Al2O3; (b) 1rGO-Al2O3; (c) 3rGO-Al2O3; (d) 5rGO-Al2O3

Fig. 4 Mechanical properties of rGO-Al2O3 ceramic composites (a) Density; (b) Vickers hardness; (c) Flexural strength; (d) Fracture toughness

Table 1 Characteristics and properties of the graphene-Al2O3 ceramic composites[11,28 -30]

Material	Filler loading/ % (in mass)	Sintering method	Vickers hardness/ GPa	Fracture toughness/ (MPa·m^1/2)	Flexural strength/ MPa	Reference
rGO-Al₂O₃	1.0	SPS	19.71	4.4	428	This work
rGO-Al₂O₃	3.0	HP	9.9	—	313.75	[11]
GO-Al₂O₃	0.5	SPS	18.3	5.4	—	[28]
FLG-Al₂O₃	1.0	SPS	20.1	3.3	310	[29]
GNP-Al₂O₃	0.5	HP	17	5.5	390	[30]

Fig. 5 Crack propagation and toughening mechanisms in rGO-Al2O3 ceramic composites

Fig. 6 (a) Electrical conductivity of rGO-Al2O3 composites as a function of filler fraction in two directions; (b) Fitting curves of electrical conductivity with inset showing the logarithmic plots of electrical conductivities against (Vh-Vh,c)

Fig. S1 (a) SEM image of obtained GO sheets; (b) XRD patterns of GO and original graphite powders

Fig. S2 TGA curves of GO and GO-Al2O3 precursor in N2 atmosphere

Fig. S3 (a-c) Sintering curves of 5rGO-Al2O3 composite ceramics and (d) bulk density of specimen sintered at different temperatures (a) 1300 ℃; (b) 1350 ℃; (c) 1400 ℃

Fig. S4 (a) XRD patterns of 5rGO-Al2O3 ceramics at different temperatures and (b) rGO-Al2O3 ceramics with different rGO contents sintered at 1350 ℃

Fig. S5 Raman spectra of rGO-Al2O3 ceramic composites

Fig. S6 EDS mappings of rGO-Al2O3 ceramic composites

Fig. S7 Thermal conductivities of rGO-Al2O3 ceramic composites

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吸附-沉淀自组装结合放电等离子烧结法制备石墨烯增强氧化铝复合陶瓷

Fabrication of Graphene-reinforced Alumina Ceramic Composites via Adsorption-precipitation Self-assembly Combined with Spark Plasma Sintering

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