多尺度类贝壳珍珠质结构层状与梯度仿生陶瓷-树脂复合材料

doi:10.15541/jim20250341

摘要/Abstract

摘要： 陶瓷材料因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位置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 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 useful reference and guidance for the structural design of strong and tough bioinspired ceramic-polymer composites.

Key words: ceramic-polymer composites, bioinspired design, multiscale structures, 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结构层状与梯度仿生陶瓷-树脂复合材料[J]. 无机材料学报, DOI: 10.15541/jim20250341.

GAO Kefeng, HE Xixi, LIU Zengqian, ZHANG Zhefeng. Bioinspired Nacre-like Ceramic-Polymer Composites with Multiscale Layered and Gradient Structures[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250341.

参考文献

[1] WILMERS J, BARGMANN S.Nature’s design solutions in dental enamel: uniting high strength and extreme damage resistance.Acta Biomaterialia, 2020, 107: 1.
[2] WANG R, GUPTA H S.Deformation and fracture mechanisms of bone and nacre.Annual Review of Materials Research, 2011, 41(1): 41.
[3] MEYERS M A, CHEN P Y, LOPEZ M I,et al. Biological materials: a materials science approach. Journal of the Mechanical Behavior of Biomedical Materials, 2011, 4(5): 626.
[4] JI B, GAO H.Mechanical properties of nanostructure of biological materials.Journal of the Mechanics and Physics of Solids, 2004, 52(9): 1963.
[5] LE FERRAND H, BOUVILLE F, NIEBEL T P, et al. Magnetically assisted slip casting of bioinspired heterogeneous composites. Nature Materials, 2015, 14(11): 1172.
[6] BARTHELAT F, YIN Z, BUEHLER M J.Structure and mechanics of interfaces in biological materials.Nature Reviews Materials, 2016, 1(4): 16007.
[7] DASTJERDI A K, RABIEI R, BARTHELAT F.The weak interfaces within tough natural composites: experiments on three types of nacre.Journal of the Mechanical Behavior of Biomedical Materials, 2013, 19: 50.
[8] BARTHELAT F, TANG H, ZAVATTIERI P D,et al. On the mechanics of mother of pearl: a key feature in the material hierarchical structure. Journal of the Mechanics and Physics of Solids, 2007, 55(2): 306.
[9] TAN G, ZHANG J, ZHENG L,et al. Nature-inspired nacre-like composites combining human tooth-matching elasticity and hardness with exceptional damage tolerance. Advanced Materials, 2019, 31(52): 1904603.
[10] LIU Y Y, XIE X, LIU Z Q,et al. Metal matrix composites reinforced by MAX phase ceramics: fabrication, properties and bioinspired designs. Journal of Inorganic Materials, 2024, 39(2): 145.
[11] ZHANG H, MA Y, WANG Y,et al. Rational design of soft-hard interfaces through bioinspired engineering. Small, 2023, 19(1): 2204498.
[12] MUNCH E, LAUNEY M E, ALSEM D H,et al. Tough, bio-inspired hybrid materials. Science, 2008, 322(5907): 1516.
[13] ZHANG N, TONG Y, XIE X,et al. Bioinspired ceramic-polymer composites with hierarchical nacre-mimetic structure via accumulative rolling technique. Ceramics International, 2023, 49(21): 33851.
[14] NIEBEL T P, BOUVILLE F, KOKKINIS D,et al. Role of the polymer phase in the mechanics of nacre-like composites. Journal of the Mechanics and Physics of Solids, 2016, 96: 133.
[15] WAN H, LEUNG N, ALGHARAIBEH S,et al. Cost-effective fabrication of bio-inspired nacre-like composite materials with high strength and toughness. Composites Part B: Engineering, 2020, 202: 108414.
[16] LOPEZ M I, MARTINEZ P E M, MEYERS M A. Organic interlamellar layers, mesolayers and mineral nanobridges: contribution to strength in abalone (Haliotis rufescence) nacre.Acta Biomaterialia, 2014, 10(5): 2056.
[17] LIU Y Y, LIU Z Q, LIU Z Y,et al. Nature inspires new high-performance metal composites. Interdisciplinary Materials, 2025, 4(3): 502.
[18] NEPAL D, KANG S, ADSTEDT K M,et al. Hierarchically structured bioinspired nanocomposites. Nature Materials, 2023, 22(1): 18.
[19] WEAVER J C, WANG Q, MISEREZ A,et al. Analysis of an ultra hard magnetic biomineral in chiton radular teeth. Materials Today, 2010, 13(1): 42.
[20] RAABE D, SACHS C, ROMANO P.The crustacean exoskeleton as an example of a structurally and mechanically graded biological nanocomposite material.Acta Materialia, 2005, 53(15): 4281.
[21] MISEREZ A, SCHNEBERK T, SUN C,et al. The transition from stiff to compliant materials in squid beaks. Science, 2008, 319(5871): 1816.
[22] ZHANG Z B, GAO H L, WEN S M,et al. Scalable manufacturing of mechanical robust bioinspired ceramic-resin composites with locally tunable heterogeneous structures. Advanced Materials, 2023, 35(14): 2209510.
[23] PRAGYA A, GHOSH T K.Soft functionally gradient materials and structures-natural and manmade: a review.Advanced Materials, 2023, 35(49): 2300912.
[24] KOKKINIS D, BOUVILLE F, STUDART A R.3D printing of materials with tunable failure via bioinspired mechanical gradients.Advanced Materials, 2018, 30(19): 1705808.
[25] WEN S M, CHEN S M, GAO W,et al. Biomimetic gradient bouligand structure enhances impact resistance of ceramic-polymer composites. Advanced Materials, 2023, 35(21): 2211175.
[26] WU Z, PAN H, HUANG P,et al. Biomimetic mechanical robust cement-resin composites with machine learning-assisted gradient hierarchical structures. Advanced Materials, 2024, 36(35): 2405183.
[27] ZHANG N, LIU Z Q, YU Q T,et al. On the damage tolerance of bioinspired gradient composites with nacre-Like architecture. Advanced Functional Materials, 2025, 35(14): 2421057.
[28] ZHANG N, LIU Z Q, DU Y B,et al. Facile processing of oriented macro-porous ceramics with high strength and low thermal conductivity. Journal of the European Ceramic Society, 2022, 42(15): 7196.
[29] Committee E08 on Fatigue and Fracture. Standard Test Method for Measurement of Fracture Toughness: ASTM E1820-13. West Conshohocken, PA: ASTM International, 2013.
[30] BAI H, WALSH F, GLUDOVATZ B,et al. Bioinspired hydroxyapatite/poly (methyl methacrylate) composite with a nacre-mimetic architecture by a bidirectional freezing method. Advanced Materials, 2016, 28(1): 50.
[31] ALHOTAN A, YATES J, ZIDAN S,et al. Flexural strength and hardness of filler-reinforced PMMA targeted for denture base application. Materials, 2021, 14(10): 2659.
[32] YERLIYURT K, TASDELEN T B, EGRI O,et al. Flexural properties of heat-polymerized PMMA denture base resins reinforced with fibers with different characteristics. Polymers, 2023, 15(15): 3211.
[33] MAGRINI T, MOSER S, FELLNER M,et al. Transparent nacre-like composites toughened through mineral bridges. Advanced Functional Materials, 2020, 30(27): 2002149.
[34] GOUJAT A, ABOUELLEIL H, COLON P,et al. Mechanical properties and internal fit of 4 CAD-CAM block materials. The Journal of Prosthetic Dentistry, 2018, 119(3): 384.
[35] HAMPE R, THEELKE B, LUMKEMANN N,et al. Fracture toughness analysis of ceramic and resin composite CAD/CAM material. Operative Dentistry, 2019, 44(4): E190-E201.
[36] Lucsanszky I J R, Ruse N D. Fracture toughness, flexural strength, and flexural modulus of new CAD/CAM resin composite blocks.Journal of Prosthodontics, 2020, 29(1): 34.
[37] 刘丽杨, 郭佳杰, 杜亚鑫, 等. 3种可切削树脂陶瓷复合材料机械性能比较. 上海口腔医学, 2019, 28(1): 25.