多尺度类贝壳珍珠质层状与梯度结构仿生陶瓷-树脂复合材料

doi:10.15541/jim20250341

无机材料学报 ›› 2026, Vol. 41 ›› Issue (5): 573-582.DOI: 10.15541/jim20250341 CSTR: 32189.14.10.15541/jim20250341

多尺度类贝壳珍珠质层状与梯度结构仿生陶瓷-树脂复合材料

高科丰¹^,²(), 何昕昕¹^,², 刘增乾¹^,²(), 张哲峰¹^,²

¹ 中国科学院金属研究所, 沈阳 110016
² 中国科学技术大学材料科学与工程学院, 沈阳 110016

收稿日期:2025-08-19 修回日期:2025-10-21 出版日期:2026-05-20 网络出版日期:2025-10-31
通讯作者: 刘增乾, 研究员. E-mail: zengqianliu@imr.ac.cn
作者简介:高科丰(1997-), 男, 博士研究生. E-mail: kfgao22b@imr.ac.cn
基金资助:
国家重点研发计划(2020YFA0710404);国家自然科学基金(52173269);国家自然科学基金(52471152)

Bioinspired Nacre-like Ceramic-polymer Composites with Multiscale Layered and Gradient Structures

GAO Kefeng¹^,²(), HE Xinxin¹^,², LIU Zengqian¹^,²(), ZHANG Zhefeng¹^,²

¹ Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
² School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China

Received:2025-08-19 Revised:2025-10-21 Published:2026-05-20 Online:2025-10-31
Contact: LIU Zengqian, professor. E-mail: zengqianliu@imr.ac.cn
About author:GAO Kefeng (1997-), male, PhD candidate. E-mail: kfgao22b@imr.ac.cn
Supported by:
National Key R&D Program of China(2020YFA0710404);National Natural Science Foundation of China(52173269);National Natural Science Foundation of China(52471152)

摘要/Abstract

摘要：

陶瓷材料的本征脆性及对结构缺陷的高度敏感, 严重制约了其在结构承载、抗冲击以及复杂服役环境中的广泛应用。以贝壳为代表的天然生物陶瓷材料在长期演变中形成了复杂而精巧的多尺度结构, 兼具高强度和韧性, 可为人造陶瓷材料设计提供重要启示。本研究利用坯体累积叠轧技术结合逐层构筑工艺, 制备得到具有多尺度类贝壳珍珠质层状与梯度结构的仿生陶瓷-树脂复合材料。该材料在微观尺度上呈现出类似天然贝壳的“砖-泥”结构, 在介观尺度上则表现为陶瓷相含量沿厚度方向呈周期性交替或梯度变化, 从而构建出多尺度层状与梯度仿生结构。本研究系统评估了仿生材料的力学性能, 并与组成相一致的均质结构进行对比, 揭示了仿生结构、力学性能及损伤机制之间的内在联系。结果显示, 多尺度层状与梯度结构仿生材料沿厚度方向呈现出高达数倍的硬度和弹性模量差异。特别是具有“软-硬-软”梯度结构的仿生材料表现出更优的强度-韧性协同效应, 其强度、断裂功、断裂与冲击韧性均显著高于相同陶瓷含量的均匀材料, 这主要归因于该结构能够有效拓宽应力分布范围, 减轻局部应力集中, 并促进机械能的广泛耗散。本研究有望为高强韧仿生陶瓷-树脂复合材料的结构优化设计提供理论依据与方法参考。

关键词: 陶瓷-树脂复合材料, 仿生设计, 多尺度结构, 梯度, 力学性能

Abstract:

Due to their intrinsic brittleness and high sensitivity to structural flaws, ceramics face a fundamental limitation in applications that require mechanical load-bearing capacity, impact resistance, and reliable performance under complex service conditions. Natural ceramic-based materials, such as nacre, have evolved intricate multiscale structures through long-term evolutionary processes, effectively integrating high strength and fracture toughness, offering valuable inspiration for the design of synthetic ceramics. This study utilized an accumulative rolling technique combined with a layer-by-layer assembly process to fabricate bioinspired ceramic-polymer composites featuring nacre-like layered and gradient structures at the multiscale. The composites exhibit a characteristic nacre-like “brick-and-mortar” architecture at the microscale, as well as periodic or gradient variations in ceramic content at the mesoscale, collectively forming bioinspired multiscale layered and gradient structures. The mechanical properties of the bioinspired composites were systematically investigated and compared with uniform composites with equivalent ceramic content. The relationships between the bioinspired structures, mechanical properties, and damage characteristics were elucidated. The results demonstrate that the bioinspired composites exhibit variations of up to several times in local hardness and elastic modulus along the thickness direction. In particular, the gradient composite with a “soft-hard-soft” configuration achieves superior strength-toughness synergy, demonstrating significantly higher strength, work of fracture, and fracture and impact toughness compared to the uniform materials with the same ceramic content. This enhancement is primarily attributed to the ability of this architecture to broaden stress distribution, reduce local stress concentrations, and facilitate extensive dissipation of mechanical energy. This study provides a useful reference and guidance for the structural design of strong and tough bioinspired ceramic-polymer composites.

Key words: ceramic-polymer composite, bioinspired design, multiscale structure, gradient, mechanical property

中图分类号:

TB332

高科丰, 何昕昕, 刘增乾, 张哲峰. 多尺度类贝壳珍珠质层状与梯度结构仿生陶瓷-树脂复合材料[J]. 无机材料学报, 2026, 41(5): 573-582.

GAO Kefeng, HE Xinxin, LIU Zengqian, ZHANG Zhefeng. Bioinspired Nacre-like Ceramic-polymer Composites with Multiscale Layered and Gradient Structures[J]. Journal of Inorganic Materials, 2026, 41(5): 573-582.

图/表 6

图1 仿生陶瓷-树脂复合材料的制备过程示意图和微观“砖-泥”结构的形成机制

Fig. 1 Schematic illustration of the fabrication procedure of the bioinspired nacre-like ceramic-polymer composites and the formation mechanism of the brick-and-mortar structure (a) Schematic of the accumulative rolling process; (b) Thin sheets with varying graphite flake contents produced via rolling; (c) Stacking configurations of thin sheets for the fabrication of bioinspired multiscale layered and gradient composites; (d) Microstructure of the porous ceramic scaffold; (e) Infiltration of the scaffold with liquid monomers; (f) Nanoscale structure of the resulting bioinspired composites

图2 仿生陶瓷-树脂复合材料在厚度截面上的微观结构

Fig. 2 Microstructures on the through-thickness cross section of bioinspired nacre-like ceramic-polymer composites (a) Through-thickness 3D XRT images (L1, G2) and SEM images (L2, G1) of bioinspired composites; (b) Representative SEM images of mesoscale layers with varying ceramic contents; (c) SEM image of the interface between layers with different ceramic contents; (d, e) Magnified SEM images of mineral bridges (d) and nanoasperities (e) on the ceramic platelets

图3 仿生陶瓷-树脂复合材料的纳米压痕硬度H和模量E沿厚度方向的变化

Fig. 3 Variations in local mechanical properties of nanoindentation hardness H and modulus E across the thickness direction of bioinspired nacre-like ceramic-polymer composites (a, b) Local variations in nanoindentation hardness (a) and modulus (b) in the L1 and L2 composites; (c, d) Local variations of nanoindentation hardness (c) and modulus (d) in the G1 and G2 composites. Colorful figures are available on website

图4 仿生陶瓷-树脂复合材料的力学性能及其与均匀材料的比较

Fig. 4 Mechanical properties of bioinspired ceramic-polymer composites compared with uniform composite (a) Representative load-displacement curves of composites in three-point bending tests; (b, c) Corresponding nominal flexural strength (b) and work of fracture (c) of composites; (d, e) Representative fracture morphologies of uniform (d) and G2 (e) composites after flexural testing; (f) Representative load-displacement curves of composites in SENB tests; (g, h) Plain-strain fracture toughness for crack initiation KIC (g) and impact toughness αk (h) of composites

图5 G2梯度材料在无缺口和存在单边缺口的三点弯曲条件下的范式等效应力与应变分布的有限元模拟结果及其与均匀材料的比较

Fig. 5 Finite element modelling simulation results of the von Mises stress and strain distributions in bioinspired G2 composite compared with uniform composite (a, b) Distributions of von Mises stress (a) and strain (b) in the bioinspired G2 and uniform composites under three-point bending; (c, d) Distributions of von Mises stress (c) and strain (d) in the bioinspired G2 and uniform composites under single-edge notched bending

图6 仿生材料与其他陶瓷-树脂复合材料的性能比较

Fig. 6 Comparison of mechanical properties between bioinspired composites and other ceramic-polymer composites (a) Variation of flexural strength as a function of the content of inorganic phase in PMMA-based ceramic-polymer composites; (b) Comparison of flexural strength and fracture toughness KIC between current bioinspired composites and other ceramic-polymer composites for dental restoration

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多尺度类贝壳珍珠质层状与梯度结构仿生陶瓷-树脂复合材料

Bioinspired Nacre-like Ceramic-polymer Composites with Multiscale Layered and Gradient Structures

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