Ezgi D. Yilmaz

Organically linked iron oxide nanoparticle supercrystals with exceptional isotropic mechanical properties

It is commonly accepted that the combination of the anisotropic shape and nanoscale dimensions of the mineral constituents of natural biological composites underlies their superior mechanical properties when compared to those of their rather weak mineral and organic constituents. Here, we show that the self-assembly of nearly spherical iron oxide nanoparticles in supercrystals linked together by a thermally induced crosslinking reaction of oleic acid molecules leads to a nanocomposite with exceptional bending modulus of 114 GPa, hardness of up to 4 GPa and strength of up to 630 MPa. By using a nanomechanical model, we determined that these exceptional mechanical properties are dominated by the covalent backbone of the linked organic molecules. Because oleic acid has been broadly used as nanoparticle ligand, our crosslinking approach should be applicable to a large variety of nanoparticle systems.

Influence of structural hierarchy on the fracture behaviour of tooth enamel

Tooth enamel has the critical role of enabling the mastication of food and also of protecting the underlying vital dentin and pulp structure. Unlike most vital tissue, enamel has no ability to repair or remodel and as such has had to develop robust damage tolerance to withstand contact fatigue events throughout the lifetime of a species. To achieve such behaviour, enamel has evolved a complex hierarchical structure that varies slightly between different species. The major component of enamel is apatite in the form of crystallite fibres with a nanometre-sized diameter that extend from the dentin–enamel junction to the oral surface. These crystallites are bound together by proteins and peptides into a range of hierarchical structures from micrometre diameter prisms to 50–100 μm diameter bundles of prisms known as Hunter–Schreger bands. As a consequence of such complex structural organization, the damage tolerance of enamel increases through various toughening mechanisms in the hierarchy but at the expense of fracture strength. This review critically evaluates the role of hierarchy on the development of the R-curve and the stress–strain behaviour. It attempts to identify and quantify the multiple mechanisms responsible for this behaviour as well as their impact on damage tolerance.

Damage modeling of small-scale experiments on dental enamel with hierarchical microstructure

Dental enamel is a highly anisotropic and heterogeneous material, which exhibits an optimal reliability with respect to the various loads occurring over years. In this work, enamels microstructure of parallel aligned rods of mineral fibers is modeled and mechanical properties are evaluated in terms of strength and toughness with the help of a multiscale modeling method. The established model is validated by comparing it with the stress-strain curves identified by microcantilever beam experiments extracted from these rods. Moreover, in order to gain further insight in the damage-tolerant behavior of enamel, the size of crystallites below which the structure becomes insensitive to flaws is studied by a microstructural finite element model. The assumption regarding the fiber strength is verified by a numerical study leading to accordance of fiber size and flaw tolerance size, and the debonding strength is estimated by optimizing the failure behavior of the microstructure on the hierarchical level above the individual fibers. Based on these well-grounded properties, the material behavior is predicted well by homogenization of a representative unit cell including damage, taking imperfections (like microcracks in the present case) into account.

Uniaxial compressive behavior of micro-pillars of dental enamel characterized in multiple directions

In this work, the compressive elastic modulus and failure strength values of bovine enamel at the first hierarchical level formed by hydroxyapatite (HA) nanofibers and organic matter are identified in longitudinal, transverse and oblique direction with the uniaxial micro-compression method. The elastic modulus values (∼70 GPa) measured here are within the range of results reported in the literature but these values were found surprisingly uniform in all orientations as opposed to the previous nanoindentation findings revealing anisotropic elastic properties in enamel. Failure strengths were recorded up to ∼1.7 GPa and different failure modes (such as shear, microbuckling, fiber fracture) governed by the orientation of the HA nanofibers were visualized. Structural irregularities leading to mineral contacts between the nanofibers are postulated as the main reason for the high compressive strength and direction-independent elastic behavior on enamels first hierarchical level.

Micromechanical characterization of prismless enamel in the tuatara, Sphenodon punctatus.

Dental enamel - a naturally occurring biocomposite of mineral and protein - has evolved from a simple prismless to an advanced prismatic structure over millions of years. Exploring the mechanical function of its structural features with differing characteristics is of great importance for evolutionary developmental studies as well as for material scientists seeking to model the mechanical performance of biological materials. In this study, mechanical properties of prismless tuatara Sphenodon punctatus enamel were characterized. Using micro-cantilever bending samples the fracture strength and elastic modulus were found to be 640 ± 87 MPa and 42 ± 6 GPa, respectively in the orientation parallel to the crystallite long axis, which decreased in the orthogonal direction. The intrinsic fracture toughness of tuatara enamel ranged from 0.21 MPa m(1/2) and 0.32 MPa m(1/2). These values correspond to the lower limit of the range of values observed in prismatic enamel at the hierarchical level 1.

Mechanical behavior of enamel rods under micro-compression.

Exploring the structural strategies behind the optimized mechanical performance of hierarchical materials has been a focal point of extensive research over the past decades. Dental enamel is one such natural material, comprising a complicated hierarchical structure with a high level of mineral content. Bundles of hydroxyapatite nanofibers (level-1) Ø: 50nm form enamel rods (level-2) Ø: 5µm, which constitute bands (level-3) Ø: 50µm. While a number of studies in the last decade using advanced fracture mechanical methods have revealed an increasing trend in the fracture toughness of enamel with each additional level of hierarchy, there is still no general agreement on how hierarchical structuring affects the stiffness and strength of enamel. In this study, we identified the stiffness and strength values of the isolated rods (level-2) via micro-compression. The rods were tested in three different orientations with respect to the loading direction: parallel, perpendicular and oblique. The highest stress level withstood before catastrophic fracture was observed to be ~1500MPa in perpendicular orientation. In the oblique loading, the specimens failed by shearing and exhibited a damage-tolerant deformation behavior, which was attributed to the conjugation spots identified between the rods and interrod sheets. The elastic modulus was ~60GPa on average and similar in all orientations. The isotropy in stiffness was attributed to the mineral contacts residing between rods. This was verified by an analytical model derived for level-1 and extended over higher hierarchical levels. The experimental results obtained at level-2 were comparable to the compressive strength and stiffness values reported for level-1 and bulk enamel in the literature. In general, our results suggest that hierarchy has only a minor influence on the compressive properties of enamel.

Exceptionally strong, stiff and hard hybrid material based on an elastomer and isotropically shaped ceramic nanoparticles

In this work the fabrication of hard, stiff and strong nanocomposites based on polybutadiene and iron oxide nanoparticles is presented. The nanocomposites are fabricated via a general concept for mechanically superior nanocomposites not based on the brick and mortar structure, thus on globular nanoparticles with nanosized organic shells. For the fabrication of the composites oleic acid functionalized iron oxide nanoparticles are decorated via ligand exchange with an α,ω-polybutadiene dicarboxylic acid. The functionalized particles were processed at 145 °C. Since polybutadiene contains double bonds the nanocomposites obtained a crosslinked structure which was enhanced by the presence of oxygen or sulfur. It was found that the crosslinking and filler percolation yields high elastic moduli of approximately 12–20 GPa and hardness of 15–18 GPa, although the polymer volume fraction is up to 40%. We attribute our results to a catalytically enhanced crosslinking reaction of the polymer chains induced by oxygen or sulfur and to the microstructure of the nanocomposite.

On the systematic documentation of the structural characteristics of bovine enamel: A critic to the protein sheath concept

The common structural description of bovine enamel used in materials science studies - nano-sized hydroxyapatite crystallites form micron-sized prisms surrounded by protein sheaths, which in turn build a complex decussation pattern - overlook many important morphological information. This hampers the correct interpretation of the data determined by mechanical analysis. For a profound structural description of enamel morphology, the visualization of its building blocks by high-resolution electron microscopy and focused-ion beam tomography technique, which reveals their form, orientation and configuration at different regions of a tooth (cut in different directions), is undertaken in this work. We adapted here the paleontological classification system and terminology developed for the description of enamel microstructures seen in different species, and accordingly documented the morphological singularities of bovine incisor enamel. The appearance of the boundary regions between crystallites and prisms contradicts to the well-known protein sheath concept. Neighboring crystallites and prisms are not separated by prominent gap zones but they are largely in contact with each other. Proteins might exist within the pores of 20-30nm in size, which are distributed inhomogeneously through the boundary regions, rather than as protein sheaths covering each crystallite and prism.