Fracture behavior of brittle ceramics at the nanoscale

In spite of the excellent properties such as high hardness, low thermal expansion, enhanced resistance to chemical degradation and superior mechanical behavior at elevated temperature, ceramic materials usually suffer from the brittle fracture and catastrophic failure, which restrict them from being used for structural applications. While a number of researchers have strived to overcome this drawback of ceramic materials by constructing the microstructures that interfere with crack growth, recent theoretical and computational studies proposed another effective method to suppress the rapid crack propagation by reducing the specimen size down to the nanometer scale. In this study, we investigated the mechanical properties of brittle ceramics by changing sample sizes from bulk to nanoscale with particular focus on their fracture failure. For the ease of analysis, we chose the isotropic, homogeneous and purely brittle material, i.e., diamond-like carbon. In-situ fixed-ends bending experiments were conducted with different beam thicknesses and lengths, 1μm ~ 100nm and 3μm ~ 6μm, respectively. Additionally, in order to demonstrate the feasibility to intactly transfer the superior properties emergent only at the nanoscale to the macroscopically available form, we fabricated the large-area 3D hierarchical hollow ceramic nano-architectures using proximity nano-patterning technique

Stabilized Amorphous Calcium Carbonate as a Precursor of Microcoating on Calcite

Highly controlled biomineralization of calcium carbonate is via non-classical mesocrystallization of amorphous precursors. In the present study, a simple in vitro assay was developed to mimic the biological process, which involved stabilized amorphous calcium carbonate and a single crystal substrate of calcite. The microcoating layer formed on the calcite substrate displayed mesocrystalline characteristics, and the layers near the substrate were strongly influenced by the epitaxy to the substrate. This behavior was preserved even when the morphology of the coating layer was modified with poly(acrylic acid), a model anionic macromolecule. Interestingly, the extent of the epitaxy increased substantially with poly(ethylene imine), which barely affected the crystal morphology. The in vitro assay in the present study will be useful in the investigations of the biomineralization and bioinspired crystallization of calcium carbonate in general

Conductivity Enhancement of Nickel Oxide by Copper Cation Codoping for Hybrid Organic-Inorganic Light-Emitting Diodes

We demonstrate a Cu­(I) and Cu­(II) codoped nickel­(II) oxide (NiO_<i>x</i>) hole injection layer (HIL) for solution-processed hybrid organic-inorganic light-emitting diodes (HyLEDs). Codoped NiO_<i>x</i> films show no degradation on optical properties in the visible range (400–700 nm) but have enhanced electrical properties compared to those of conventional Cu­(II)-only doped NiO_<i>x</i> film. Codoped NiO_<i>x</i> film shows an over four times increased vertical current in comparison with that of NiO_<i>x</i> in conductive atomic force microscopy (c-AFM) configuration. Moreover, the hole injection ability of codoped NiO_<i>x</i> is also improved, which has ionization energy of 5.45 eV, 0.14 eV higher than the value of NiO_<i>x</i> film. These improvements are a consequence of surface chemical composition change in NiO_<i>x</i> due to Cu cation codoping. More off-stoichiometric NiO_<i>x</i> formed by codoping includes a large amount of Ni vacancies, which lead to better electrical properties. Density functional theory calculations also show that Cu doped NiO model structure with Ni vacancy contains diverse oxidation states of Ni based on both density of states and partial atomic charge analysis. Finally, HyLEDs of Cu codoped NiO_<i>x</i> HIL have higher performance comparing with those of pristine NiO_<i>x</i>. The current efficiency of devices with NiO_<i>x</i> and codoped NiO_<i>x</i> HIL are 11.2 and 15.4 cd/A, respectively. Therefore, codoped NiO_<i>x</i> is applicable to various optoelectronic devices due to simple sol–gel process and enhanced doping efficiency