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.     

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.     

生物矿化在仿生材料领域的研究进展

生物矿化重要的特征之一是无机矿物在细胞分泌的有机基质调节下成核和生长,最终形成具有特殊组装方式和多级结构特点的生物矿化材料,如骨、牙和贝壳等。仿生合成是近年来受生物矿化原理启示而发展起来的一个崭新领域,其合成过程具有高效、有序及自动化等特点。仿生合成材料是具有特殊性能的新型材料,有着潜在的广阔应用前景。综述了近年来在仿骨、仿牙和仿贝壳珍珠层等仿生材料、晶体工程、涂层及在防治病理矿化疾病等方面的研究进展。     

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。      

珍珠的成分、微结构及成因研究

综述了现有珍珠中无机成分、有机质、微量元素、珍珠层仿生学等相关研究领域的进展,重点探讨了结晶多型与无机相转变、有机质作用、微环境影响等问题。珍珠微结构成因理论包括"隔室"说、矿物桥说、模板说、多模板成因说等,在研究珍珠层形成机制时应综合考虑微环境、有机质及无机成分在无机晶体成核、结晶、长大各个阶段所起的作用。     

贝壳珍珠层生物矿化及其对仿生材料的启示

贝壳珍珠层作为一种典型的生物矿化材料而备受关注. 本文综述了贝壳珍珠层结构及其文石晶体的结晶学取向, 概述了贝壳珍珠层成因的生物矿化机理. 同时介绍了贝壳珍珠层特殊的组装方式在仿生材料方面近年来的研究进展, 认为选择合适的有机物,使其自组装成各种超分子结构作为无机物沉积的模板, 是仿生合成的关键.     

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.     

淡水养殖珍珠中文石板片厚度的变化及其微结构分析

通过场发射扫描电镜(FE-SEM),对白、粉和紫3种颜色的淡水养殖珍珠的珍珠层微结构进行了较系统研究。结果表明,在白色、粉色及紫色3种色系的珍珠中,在沿珍珠的半径方向上,珍珠层板片的厚度是变化的,且离珍珠核心距离越远,文石板片的厚度逐渐变薄;在同一直径不同颜色的珍珠中,接近珍珠外表面区域内珍珠层文石板片的厚度及珍珠外表面"梯田式"结构形貌也存在明显的差异,且珍珠表面"梯田式"结构越致密,其近珍珠表面的文石板片的厚度就越薄。     

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.     

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.     

On the nature of the stiffness of nacre

The high stiffness of the biogenic composite nacre has to be attributed to the particular microstructure consisting of mineral platelets and the interfacial organic phase. In order to understand the mechanisms being responsible the elastic properties of nacre under tensile and shear loads have been studied and numerically simulated. It is found, that the thin layer of biopolymer plays a key role for the stress distribution in the composite. Two types of mechanisms of load transfer between the mineral platelets are discussed. Their plausibility is discussed for different levels of the Poisson's ratio of the biopolymer. Finite element calculations show, that the high stiffness of nacre determined experimentally is only approached if the organic layers participate as incompressible interphase on the deformation of the composite. In addition, mineral bridges between adjacent platelets enhance the stiffness of nacre under shear and transversal tension.     

贝壳珍珠层层间断口及死亡期的XPS研究

利用X射线光电子能谱(XPS),对贝壳珍球层层间断口进行了研究,探讨了有机物的元素组成及其随死亡期的变化.研究结果表明:贝壳珍珠层层间都含有C、Ca、N、O这四种元素,还有少量的S元素,有机质元素含量为C(67.50),O(17.68),N(14.24),S(0.58)at%.层间断口处有机物均匀存在于断口两侧,裂纹在有机物中的路径是曲折的,有利于增韧.对应于珍珠层力学性能随死亡期的变化,层间有机物随死亡期的延长其成份也有所变化.     

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.     

淡水三角帆蚌贝壳珍珠质的同步辐射XRD研究

利用同步辐射XRD研究淡水三角帆蚌贝壳珍珠质的内应力和珍珠质中单个文石板片的微结构, 发现淡水三角帆蚌贝壳珍珠质中单个文石板片内存在晶内有机物, 且该晶内有机物导致珍珠质层中产生拉应力. 这一拉应力沿不同晶向呈现强烈的各向异性, 表明晶内有机物在文石板片内很可能以某一特定的方式排列. 同步辐射XRD图谱的线形分析进一步证实淡水三角帆蚌贝壳珍珠质中的晶内有机物吸附于文石板片的(002)晶面. 这些研究结果将促进珍珠质矿化及强韧化机制的研究, 为设计高性能无机-有机复合材料及培育珍珠提供科学的根据.     

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.