Interface-Mediated Twinning-Induced Plasticity in a Fine Hexagonal Microstructure Generated by Additive Manufacturing.

The grain size is a determinant microstructural feature to enable the activation of deformation twinning in hexagonal close-packed (hcp) metals. Although deformation twinning is one of the most effective mechanisms for improving the strength-ductility trade-off of structural alloys, its activation is reduced with decreasing grain size. This work reports the discovery of the activation of deformation twinning in a fine-grained hcp microstructure by introducing ductile body-centered cubic (bcc) nano-layer interfaces. The fast solidification and cooling conditions of laser-based additive manufacturing are exploited to obtain a fine microstructure that, coupled with an intensified intrinsic heat treatment, permits to generate the bcc nano-layers. In situ high-energy synchrotron X-ray diffraction allows tracking the activation and evolution of mechanical twinning in real-time. The findings obtained show the potential of ductile nano-layering for the novel design of hcp damage tolerant materials with improved life spans.

High-Temperature Hydrogen Sensing Performance of Ni-Doped TiO2 Prepared by Co-Precipitation Method.

This work deals with the substantially high-temperature hydrogen sensors required by combustion and processing technologies. It reports the synthesis of undoped and Ni-doped TiO2 (with 0, 0.5, 1 and 2 mol.% of Ni) nanoparticles by a co-precipitation method and the obtained characteristics applicable for this purpose. The effect of nickel doping on the morphological variation, as well as on the phase transition from anatase to rutile, of TiO2 was investigated by scanning electron microscopy, X-ray diffraction and Raman spectroscopy. The resistive sensors prepared with these powders were tested toward H2 at 600 °C. The results indicate that 0.5% Ni-doped TiO2 with almost equal amounts of anatase and rutile shows the best H2 sensor response (ΔR/R0 = 72%), response rate and selectivity. The significant improvement of the sensing performance of 0.5% Ni-doped TiO2 is mainly attributed to the formation of the highest number of n-n junctions present between anatase and rutile, which influence the quantity of adsorbed oxygen (i.e., the active reaction site) on the surface and the conductivity of the material.

Formation and mosaicity of coccolith segment calcite of the marine algae Emiliania huxleyi.

Coccolithophores belong to the most abundant calcium carbonate mineralizing organisms. Coccolithophore biomineralization is a complex and highly regulated process, resulting in a product that strongly differs in its intricate morphology from the abiogenically produced mineral equivalent. Moreover, unlike extracellularly formed biological carbonate hard tissues, coccolith calcite is neither a hybrid composite, nor is it distinguished by a hierarchical microstructure. This is remarkable as the key to optimizing crystalline biomaterials for mechanical strength and toughness lies in the composite nature of the biological hard tissue and the utilization of specific microstructures. To obtain insight into the pathway of biomineralization of Emiliania huxleyi coccoliths, we examine intracrystalline nanostructural features of the coccolith calcite in combination with cell ultrastructural observations related to the formation of the calcite in the coccolith vesicle within the cell. With TEM diffraction and annular dark-field imaging, we prove the presence of planar imperfections in the calcite crystals such as planar mosaic block boundaries. As only minor misorientations occur, we attribute them to dislocation networks creating small-angle boundaries. Intracrystalline occluded biopolymers are not observed. Hence, in E. huxleyi calcite mosaicity is not caused by occluded biopolymers, as it is the case in extracellularly formed hard tissues of marine invertebrates, but by planar defects and dislocations which are typical for crystals formed by classical ion-by-ion growth mechanisms. Using cryo-preparation techniques for SEM and TEM, we found that the membrane of the coccolith vesicle and the outer membrane of the nuclear envelope are in tight proximity, with a well-controlled constant gap of ~4 nm between them. We describe this conspicuous connection as a not yet described interorganelle junction, the "nuclear envelope junction". The narrow gap of this junction likely facilitates transport of Ca2+ ions from the nuclear envelope to the coccolith vesicle. On the basis of our observations, we propose that formation of the coccolith utilizes the nuclear envelope-endoplasmic reticulum Ca2+ -store of the cell for the transport of Ca2+ ions from the external medium to the coccolith vesicle and that E. huxleyi calcite forms by ion-by-ion growth rather than by a nanoparticle accretion mechanism.

Interdigitating biocalcite dendrites form a 3-D jigsaw structure in brachiopod shells.

We report a newly discovered dense microstructure of dendrite-like biocalcite that is formed by marine organisms. High spatial resolution electron backscatter diffraction (EBSD) was carried out under specific analytical conditions (15 and 10 kV) on the primary layer of the modern brachiopod Gryphus vitreus. The primary layer of modern brachiopods, previously termed nanocrystalline, is formed by an array of concave/convex calcite grains with interdigitated recesses and protrusions of abutting crystals without any cavities in or between the dendrites. The interface topology of this structure ranges from a few tens of nanometres to tens of micrometres, giving a nanoscale structure to the material fabric. The dendritic grains show a spread of crystallographic orientation of several degrees and can thus be referred to as mesocrystals. Individual dendritic mesocrystals reach sizes in one dimension larger than 20 µm. The preferred crystallographic orientation is similar in the primary and adjacent fibrous shell layers, even though these two layers show completely different crystal morphologies and grain boundary topologies. This observation indicates that two separate control mechanisms are active when the primary and the fibrous shell layers are formed. We propose a growth model for the interdigitated dendritic calcite grain structure based on a precursor of vesicles filled with amorphous calcium carbonate (ACC).