Molecular origin of the sawtooth behavior and the toughness of nacre

We present in this paper a method to build a computer model that mimic the mineral–protein composite structure of a nacre tablet. Motivated by the interesting observations in AFM experiments of nacre, protein chains stretching out from grain boundaries are simulated by steered molecular dynamics (SMD) to gain an insight into the effect of protein–aragonite interaction on the mechanical properties of nacre and the molecular mechanisms of the sawtooth behavior. Force-extension curves are obtained and the key characteristics of sawtooth behavior are observed in SMD simulations in agreement with existing AFM experiments of nacre. The effect of water on protein–mineral interaction is investigated through including and excluding water molecules in the grain boundaries of the models. Different from the existing belief that protein unfolding is the origin of the “sawtooth” behavior, we have found that the electrostatic interactions between the protein and aragonite mineral are responsible for the sawtooth behavior and hence the high toughness of nacre.     

贝壳珍珠层中文石晶体择优取向研究

贝壳珍珠层中文石晶体的择优取向是其具有独特力学性能的重要原因．本文采用Ｘ射线衍射方法对我国主要育珠贝（蚌）的贝壳珍珠层中文石晶体的择优取向进行了较系统的研究,结果表明：海水马氏珍珠贝、大珠母贝及企鹅珍珠贝贝壳珍珠层中文石晶体ｃ轴垂直珍珠层面定向排列;淡水三角帆蚌壳珍珠层文石晶体有两种明显择优取向,一种ｃ轴垂直珍珠层层面,另一种ｃ轴与层面斜交,其（０１２）面网方向与层面平行．     

鲍鱼壳珍珠层无机文石片的层状微结构研究

贝壳珍珠层是软体动物壳的最内层,经过若干世纪的自然进化,贝壳珍珠层形成了优良的微结构,并使贝壳具有了相当高的强度、刚度及断裂韧性.本文利用扫描电镜(SEM)观察了鲍鱼贝壳珍珠层的主要微结构特征,发现其是由层状的无机文石片和有机胶原蛋白质组成的生物陶瓷复合材料.根据发现的贝壳珍珠层层状微结构特征,建立贝壳珍珠层三维有限元模型,并用此模型分析了珍珠层的拉伸屈服极限与无机文石片拉伸屈服极限及其厚度的关系,研究表明珍珠层的屈服极限随无机文石片屈服极限的增加和无机文石片厚度的减小而增加.     

贝壳珍珠层断裂过程的原位观察及其增韧机制分析

天然生物材料的组织结构特征及其与性能间的关系研究对于材料的仿生设计有重要意义.本文利用扫描电镜原位观察了受拉伸载荷作用下珍珠层中裂纹的萌生及扩展方式,并结合SEM和TEM技术研究了贝壳珍珠层微观组织结构,探讨了裂纹扩展过程中的增韧机制.结果表明,珍珠层相邻片层凹凸镶嵌互补,多边形文石晶体是由纳米级颗粒构成的多晶体.裂纹偏转,有机物桥联,纤维拔出,小孔聚结等多种增韧机制在裂纹扩展过程中协同作用,都源自珍珠层独特的微观结构,并提出片层的球冠型结构是导致珍珠层具有超常韧性的机制之一.     

三角帆蚌珍珠质层结构和珍珠质涂层的研究

利用扫描电镜和光学显微镜对三角帆蚌贝壳和珍珠的珍珠质层微观结构进行了分析研究, 发现贝壳的珍珠质层中存在异常的结构带, 主要有柱状珍珠质带, 针状晶体带以及棱柱状晶体带. 其中柱状珍珠质带中, 单片文石板片的厚度超过1μm, 是正常珍珠质中文石板片厚度的两倍. 而对正常珍珠的珍珠质层的大量观察却未发现类似的异常结构. 分析认为这可能是因为贝壳珍珠质的矿化微环境与珍珠的珍珠质矿化微环境不同导致的. 并利用圆柱形珍珠囊在钛金属牙种植体表面制备的珍珠质涂层具有沿整个圆周面均匀生长的特点.     

Mechanical properties of the elemental nanocomponents of nacre structure

Sheet nacre is a nanocomposite with a multiscale structure displaying a lamellar “bricks and mortar” microarchitecture. In this latter, the brick refer to aragonite platelets and the mortar to a soft organic biopolymer. However, it appears that each brick is also a nanocomposite constituted as CaCO₃ nanoparticles reinforced organic composite material. What is the role of this “intracrystalline” organic phase in the deformation of platelet? How does this nanostructure control the mechanical behaviour of sheet nacre at the macroscale? To answer these questions, the mechanical properties of each nanocomponents are successively investigated and computed using spherical and sharp nanoindentation tests combined with a structural model of the organomineral platelets built from AFM investigations.     

Why is nacre so tough and strong?

In this paper we describe the details of simulations conducted on three-dimensional finite element models of nacre integrated with experiments. This work gives an overview of modeling mechanical behavior in nacre and quantitatively elucidates the specific role of many details of structure in nacre on the stress–strain response. We describe the role of each of the details of nanostructure on the mechanics and deformation behavior of nacre as well as identify the key mechanisms responsible for the unique mechanical behavior of nacre. Nanoscale asperities and mineral contacts have marginal role on mechanical response of nacre and platelet interlocks have a significant role on deformation in nacre. We describe the key strengthening and toughening mechanisms in nacre as:

• 1.Material properties of aragonite and organic matrix, especially the unique properties of the organic phase in the confined space between platelets.
• 2.Structure at micro scale: size, shape of platelets etc.
• 3.Interlocking of aragonite platelets: progressive failure of interlocks guides the fracture path.
• 4.Molecular interactions at the organic–inorganic interface.

     

Biomimetic Pathways for Nanostructured Poly(KAMPS)/aragonite Composites that Mimic Seashell Nacre

Complex microstructures of biominerals such as seashell nacre, bone, and teeth are awe‐inspiring. Nature has devised schemes to combine hard inorganic platelets of aragonite (CaCO₃) and an organic matrix that produce tough biocomposites. The ability of the organic‐inorganic components to “slide” internally leads to the toughening of the materials, though a recreation of this system at the nanoscale has yet to be shown. Here, we implement a poly(KAMPS)‐based assembly, which is carried out entirely from dilute aqueous solutions of the materials to create a “brick and mortar”‐type aragonite structure that mimics the platelet sliding and exhibits toughening. The negatively charged poly(KAMPS) chains are attracted to the positively charged divalent cations, by which addition of NaHCO₃ to an aqueous mixture of Ca²⁺‐poly(KAMPS), results in the growth of aragonite nanorods with a width of 120 nm. The reversible nature of the physical gel formation of poly(KAMPS) in solution results in adhesion of the nanorods into a microscale structure. The new nacre‐like carbonate composite, has a modulus (44 GPa) and hardness (2.8 GPa) on a similar order as to that of nacre and other bio‐composites, exhibits limited creep, and demonstrates a mechanism with nanoscale deformation.     

Toughening mechanisms in bioinspired multilayered materials

Outstanding mechanical properties of biological multilayered materials are strongly influenced by nanoscale features in their structure. In this study, mechanical behaviour and toughening mechanisms of abalone nacre-inspired multilayered materials are explored. In nacre''s structure, the organic matrix, pillars and the roughness of the aragonite platelets play important roles in its overall mechanical performance. A micromechanical model for multilayered biological materials is proposed to simulate their mechanical deformation and toughening mechanisms. The fundamental hypothesis of the model is the inclusion of nanoscale pillars with near theoretical strength (σ_th ~ E/30). It is also assumed that pillars and asperities confine the organic matrix to the proximity of the platelets, and, hence, increase their stiffness, since it has been previously shown that the organic matrix behaves more stiffly in the proximity of mineral platelets. The modelling results are in excellent agreement with the available experimental data for abalone nacre. The results demonstrate that the aragonite platelets, pillars and organic matrix synergistically affect the stiffness of nacre, and the pillars significantly contribute to the mechanical performance of nacre. It is also shown that the roughness induced interactions between the organic matrix and aragonite platelet, represented in the model by asperity elements, play a key role in strength and toughness of abalone nacre. The highly nonlinear behaviour of the proposed multilayered material is the result of distributed deformation in the nacre-like structure due to the existence of nano-asperities and nanopillars with near theoretical strength. Finally, tensile toughness is studied as a function of the components in the microstructure of nacre.     

贝壳珍珠母增韧机理研究进展

基于国内外对贝壳材料微结构研究的实验照片与力学性能的研究成果,描述了贝壳珍珠母独特的微观结构,包括无机层与有机基质层"砖-泥"式交错层叠结构、文石层波纹表面和文石表面纳米凸起与矿物桥结构等,同时也揭示了贝壳珍珠母微结构对其韧性的增强机理。对国内力学家近年来提出的微观结构"缺陷不敏感"增韧理论进行了理论阐述。     

三角帆蚌贝壳的微结构及尺寸变化特征

天然生物经历了亿万年的不断进化,已经形成了近乎完美的结构。天然生物材料结构的研究是仿生研究的基础,本文以三角帆蚌贝壳为研究对象,利用SEM和AFM,描述了三角帆蚌贝壳的微结构特征,包括其角质层、棱柱层、珍珠层及界面和晶带的形貌,揭示文石晶片及各层间的尺寸变化规律。研究表明:角质层内部分布大量裂纹,珍珠层与棱柱层无明显过渡界面,珍珠层内发现条状晶带结构缺陷;贝壳壳体和珍珠层厚度随0生长线向外呈现先增大后减小的变化趋势,且单层文石晶片的厚度不均,最厚处可达最薄处的2倍多。对三角帆蚌贝壳的结构进行了深入研究,为其优异的力学性能提供了理论依据,为未来的仿生结构设计提供了新思路和新想法。      

25th Anniversary Article: Artificial Carbonate Nanocrystals and Layered Structural Nanocomposites Inspired by Nacre: Synthesis,Fabrication and Applications

Rigid biological systems are increasingly becoming a source of inspiration for the fabrication of next generation advanced functional materials due to their diverse hierarchical structures and remarkable engineering properties. Among these rigid biomaterials, nacre, as the main constituent of the armor system of seashells, exhibiting a well‐defined ‘brick‐and‐mortar’ architecture, excellent mechanical properties, and interesting iridescence, has become one of the most attractive models for novel artificial materials design. In this review, recent advances in nacre‐inspired artificial carbonate nanocrystals and layered structural nanocomposites are presented. To clearly illustrate the inspiration of nacre, the basic principles relating to plate‐like aragonite single‐crystal growth and the contribution of hierarchical structure to outstanding properties in nacre are discussed. The inspiration of nacre for the synthesis of carbonate nanocrystals and the fabrication of layered structural nanocomposites is also discussed. Furthermore, the broad applications of these nacre inspired materials are emphasized. Finally, a brief summary of present nacre‐inspired materials and challenges for the next generation of nacre‐inspired materials is given.     

A Nacre‐Inspired Separator Coating for Impact‐Tolerant Lithium Batteries

The commercial ceramic nanoparticle coated microporous polyolefin separators used in lithium batteries are still vulnerable under external impact, which may cause short circuits and consequently severe safety threats, because the protective ceramic nanoparticle coating layers on the separators are intrinsically brittle. Here, a nacre‐inspired coating on the separator to improve the impact tolerance of lithium batteries is reported. Instead of a random structured ceramic nanoparticle layer, ion‐conductive porous multilayers consisting of highly oriented aragonite platelets are coated on the separator. The nacre‐inspired coating can sustain external impact by turning the violent localized stress into lower and more uniform stress due to the platelet sliding. A lithium‐metal pouch cell using the aragonite platelet coated separator exhibits good cycling stability under external shock, which is in sharp contrast to the fast short circuit of a lithium‐metal pouch cell using a commercial ceramic nanoparticle coated separator.     

Micromechanical model of nacre tested in tension

A modified shear lag theory is used to model the tensile behavior of Pinctada nacre. A two-dimensional model is used to analyze the stress transfer between the aragonite platelets of nacre assuming that the ends of the platelet are not bonded with the organic matrix. Elastic-perfectly plastic behavior of the organic matrix is assumed. A model for stress transfer between the platelets when the matrix between the platelets starts behaving plastically is developed. It is assumed that nacre fails when the matrix breaks after the ultimate shear strain in the matrix is exceeded. This theory can be used to model the stress transfer in platelet reinforced composites at high volume fractions.     

贝壳珍珠层的研究现状

贝壳中的珍珠层是由占壳重95%的CaCO3晶体和占壳重仅5%的有机体构成的一种优异的天然纳米复合材料.对珍珠层的研究现状和最新进展进行了评述.重点介绍了珍珠层形成机制中的隔室说、矿物桥说、模板说和多模板二步成因假说等4种学说,及裂纹的偏转、纤维的拔出、有机质的桥连、矿物桥机制和凹凸镶嵌结构等5种增韧机理,简述了珍珠层的组成和微结构,指出了珍珠层研究中有待解决的问题.     

Observations of damage morphologies in nacre during deformation and fracture

The deformation, fracture and toughening mechanisms of nacre from a kind of fresh-water bivalve mollusc (Cristaria plicata) were studied by SEM, TEM and microindentation tests. Experimental results revealed a strong anisotropy of the damage behaviour reflecting the microstructural character of nacre. The fractured surface parallel to the cross-sectional surface of nacre was much more tortuous than that parallel to the platelet surface. The crack line on the cross-sectional surface was step-like, while that on the platelet surface was polygonal. Sliding of aragonite layer combined with the plastic deformation of organic matrix is the main plastic deformation mechanism of nacre. Three main toughening mechanisms have been found acting in concert: crack deflection, fibre pull-out and organic matrix bridging.     

Crystal orientation,toughening mechanisms and a mimic of nacre

Based on the investigations of crystal structure of nacre using SEM, TEM and XRD, it is proposed that there exists a domain structure of crystal orientation in the nacre. The orientation domain consists of continuous 3–10 tablets along the direction perpendicular to nacreous plane, and 1–5 tablets in a single lamina. The tablets in a domain are crystallographic identical in three dimensions. From the crack morphologies, it is found that the crack deflection, fibre pull-out and organic matrix bridging are the three main toughening mechanisms acting on nacre. The organic matrix plays an important role in the toughening of this biological composite. The biomimetically synthesized composite made of alumina and kevlar showed significant increase in the fracture energy compared with the single ceramics. The soluble proteins extracted from nacre can induce aragonite and the one from prism can induce calcite grown with a preferred orientation of [104]. The insoluble proteins control the nucleation site and thus lead to a finer crystallization of CaCO₃.     

Modeling mechanical responses in a laminated biocomposite

Accurate pseudo-hexagonal nanoarchitecture of nacre was used to design three dimensional finite element models of nacre, the inner layer of mollusk shells. Tensile tests were simulated introducing linear and nonlinear material properties in these models. Material parameters of components of nacre (aragonitic bricks and the complex organic phase) such as elastic modulus and hardness were obtained from bulk measurements reported in literature. In addition, nanoscale experiments conducted using atomic force microscopy and nanoindentation provided mechanical properties of aragonite platelets and organic phase. Linear simulations in the elastic regime at low stresses (2 MPa) was conducted on the new models. Our simulations indicate that a high modulus of organic phase ( 20 GPa) is necessary to obtain the experimentally obtained bulk phase elastic response of nacre. Our nanoindentation experiments also confirmed the simulations. Further nonlinear simulations were conducted under the assumption of a fully elastic behavior of aragonite and an elastoplastic model for the organic phase. Further the yield stress of the organic phase is varied over a wide range from 40 to 400 MPa. The resulting yield stress of nacre was compared to experimentally obtained value. Again our simulations indicate that an exceptionally high yield stress of the organic phase is necessary to obtain the yield behavior in nacre. Further, nanostructural nuances in the form of platelet-platelet mineral contacts were incorporated in the three dimensional models. The role of these mineral contacts on linear and nonlinear responses under high and low loads was quantitatively evaluated. Our simulations indicate for the first time that presence of these mineral contacts has minimal effect on both linear and nonlinear responses in nacre. As a matter of fact, the contacts are regions of high stress concentration and they break long before yield begins in nacre ( 50 MPa). These results have significant ramifications on a biomimetic design of scalable nanocomposites mimicking nacre.     

On flaw tolerance of nacre: a theoretical study

As a natural composite, nacre has an elegant staggered ‘brick-and-mortar’ microstructure consisting of mineral platelets glued by organic macromolecules, which endows the material with superior mechanical properties to achieve its biological functions. In this paper, a microstructure-based crack-bridging model is employed to investigate how the strength of nacre is affected by pre-existing structural defects. Our analysis demonstrates that owing to its special microstructure and the toughening effect of platelets, nacre has a superior flaw-tolerance feature. The maximal crack size that does not evidently reduce the tensile strength of nacre is up to tens of micrometres, about three orders higher than that of pure aragonite. Through dimensional analysis, a non-dimensional parameter is proposed to quantify the flaw-tolerance ability of nacreous materials in a wide range of structural parameters. This study provides us some inspirations for optimal design of advanced biomimetic composites.     

Modeling microarchitecture and mechanical behavior of nacre using 3D finite element techniques Part I Elastic properties

Three dimensional finite element models of nacre were constructed based on reported microstructural studies on the 'brick and mortar' micro-architecture of nacre. 3D eight noded isoparametric brick elements were used to design the microarchitecture of nacre. Tensile tests were simulated using this model. The tests were conducted at low stresses of 2 MPa which occur well within the elastic regime of nacre and thus effects related to locus and extent of damage were ignored. Our simulations show that using the reported values of elastic moduli of organic (0.005 GPa) and aragonitic platelets (205 GPa), the displacements observed in nacre are extremely large and correspond to a very low modulus of 0.011 GPa. The reported elastic modulus of nacre is of the order of 50 GPa. The reason for this inconsistency may arise from two possibilities. Firstly, the organic layer due to its multilayered structure is possibly composed of distinct layers of different elastic moduli. The continuously changing elastic modulus within the organic layer may approach modulus of aragonite near the organic-inorganic interface. Simulations using variable elastic moduli for the organic phase suggest that an elastic modulus of 15 GPa is consistent with the observed elastic behavior of nacre. Another explanation for the observed higher elastic modulus may arise from localized platelet-platelet contact. Since the observed modulus of nacre lies within the above two extremes (i.e. 15 GPa and 205 GPa) it is suggested that a combination of the two possibilities, i.e. a higher modulus of the organic phase near the organic-inorganic interface and localized platelet-platelet contact can result in the observed elastic properties of nacre.