Below the Hall-Petch Limit in Nanocrystalline Ceramics.

Reducing the grain size of metals and ceramics can significantly increase strength and hardness, a phenomenon described by the Hall-Petch relationship. The many studies on the Hall-Petch relationship in metals reveal that when the grain size is reduced to tens of nanometers, this relationship breaks down. However, experimental data for nanocrystalline ceramics are scarce, and the existence of a breakdown is controversial. Here we show the Hall-Petch breakdown in nanocrystalline ceramics by performing indentation studies on fully dense nanocrystalline ceramics fabricated with grain sizes ranging from 3.6 to 37.5 nm. A maximum hardness occurs at a grain size of 18.4 nm, and a negative (or inverse) Hall-Petch relationship reduces the hardness as the grain size is decreased to around 5 nm. At the smallest grain sizes, the hardness plateaus and becomes insensitive to grain size change. Strain rate studies show that the primary mechanism behind the breakdown, negative, and plateau behavior is not diffusion-based. We find that a decrease in density and an increase in dissipative energy below the breakdown correlate with increasing grain boundary volume fraction as the grain size is reduced. The behavior below the breakdown is consistent with structural changes, such as increasing triple-junction volume fraction. Grain- and indent-size-dependent fracture behavior further supports local structural changes that corroborate current theories of nanocrack formation at triple junctions. The synergistic grain size dependencies of hardness, elasticity, energy dissipation, and nanostructure of nanocrystalline ceramics point to an opportunity to use the grain size to tune the strength and dissipative properties.

Fabrication of Photoluminescent Quantum Dot Thiol-yne Nanocomposites via Thermal Curing or Photopolymerization.

Strong, flexible, and transparent materials have garnered tremendous interest in recent years as materials and electronics manufacturers pursue devices that are bright, flexible, durable, tailorable, and lightweight. Depending on the starting components, polymers fabricated using thiol-yne chemistry have been shown to be exceptionally strong and/or flexible, while also being amenable to modification by the incorporation of nanoparticles. In the present work, novel ligands were synthesized and used to functionalize quantum dots (QDs) of various diameters. The functionalized QDs were then incorporated into thiol-yne prepolymer matrices. These matrices were subsequently polymerized to form QD thiol-yne nanocomposite polymers. To demonstrate the versatility of the fabrication process, the prepolymers were either thermally cured or photopolymerized. The resulting transparent nanocomposites expressed the size-specific color of the QDs within them when exposed to ultraviolet irradiation, demonstrating that QDs can be incorporated into thiol-yne polymers without significantly altering QD expression. With the inclusion of QDs, thiol-yne nanocomposite polymers are promising candidates for use in numerous applications including as device display materials, optical lens materials, and/or sensor materials.

Barium titanate-polymer composites produced via directional freezing.

In this study, we use a freeze casting technique to construct ceramic-polymer composites in which the 2 phases are arranged in an electrically parallel configuration. By doing so, the composites exhibit dielectric constant (K) up to 2 orders of magnitude higher than that of composites with ceramic particles randomly dispersed in a polymer matrix. In this technique, an aqueous ceramic slurry was frozen unidirectionally to form ice platelets and ceramic aggregates that were aligned in the temperature gradient direction. Upon freeze-drying, the ice platelets sublimed and left the lamellar ceramic structure intact. The green ceramic body was fired to retain the microstructure, and then the space between ceramic lamellae was infiltrated with a polymer material. The finished composites exhibit the high dielectric constant (1000) of ferroelectric ceramics while maintaining the unique properties of polymer materials such as graceful failure, low dielectric loss, and high dielectric breakdown.