Grain Boundary Migration of NiO-MgO Alloys

Grain boundary engineering offers enhanced control of microstructure development during processing, leading to improved final material properties. However, using the effects of the interfacial energy anisotropy on grain boundary mobility to control microstructure development is not well understood. The NiO-MgO system is studied as it has complete solid solubility and a transition in the faceting behavior with composition due to changes in the interfacial energy anisotropy. NiO-MgO powders were produced through the amorphous citrate process and modifications to the process were made to reduce particle and agglomerate size. The powders were pressed and sintered in various conditions to produce fine grained high purity dense samples. Wet milling demonstrated a reduction in the overall particle and agglomerate size of the powders. Pressureless sintering showed an increase in the densification of the NiO-MgO compacts with increased heating rate. Wet milling and high heating rates produced near fully dense samples with relative apparent densities of \u3e95% and open porositie

Impact of an external electric field on grain growth in oxides: Comparison of flash sintered samples to field assisted grain growth

In the last years ample effort was done to investigate the effect of electric fields on matter. We investigated the effect of an external electric field on the oxide ceramic model system strontium titanate. More precisely, we observed that a non-contacting external electric field has an impact on the defect distribution and the grain growth. Oxygen vacancies are migrating towards the negative electrode yielding a higher oxygen vacancy concentration compared to the positive electrode. As a result, faster grain growth was observed on the negative electrode. Recent thermodynamic defect calculations revealed the mechanism for this relationship [1]: A high oxygen vacancy concentration results in less space charge and, as such, in less segregation of cationic defects. As less segregation requires less diffusion for grain boundary migration, faster grain growth occurs. We extended these findings to flash sintering of doped strontium titanate. TEM imaging and EDS analysis were used to investigate the microstructure and to map the dopant segregation at the grain boundaries. Observing different dopant species (acceptors and donors) gives insight on flash sintering for different defect concentration and types with different segregation properties. In addition, field assisted microstructure evolution experiments with titania (no current, insulating electrodes) allow to apply the gained knowledge to different material systems with different defect chemistry. [1] Work of Jana P Parras and Roger A. de Souz

Nanoscale stacking fault-assisted room temperature plasticity in flash-sintered TiO2.

Ceramic materials have been widely used for structural applications. However, most ceramics have rather limited plasticity at low temperatures and fracture well before the onset of plastic yielding. The brittle nature of ceramics arises from the lack of dislocation activity and the need for high stress to nucleate dislocations. Here, we have investigated the deformability of TiO2 prepared by a flash-sintering technique. Our in situ studies show that the flash-sintered TiO2 can be compressed to ~10% strain under room temperature without noticeable crack formation. The room temperature plasticity in flash-sintered TiO2 is attributed to the formation of nanoscale stacking faults and nanotwins, which may be assisted by the high-density preexisting defects and oxygen vacancies introduced by the flash-sintering process. Distinct deformation behaviors have been observed in flash-sintered TiO2 deformed at different testing temperatures, ranging from room temperature to 600°C. Potential mechanisms that may render ductile ceramic materials are discussed

Flash Sintering of Zinc Oxide and the Growth of its Nanostructures

Flash sintering was first demonstrated in 2010, where a ceramic green body was rapidly densified within seconds by applying an electric field during the heating process. The ultra-fast densification can occur as current abruptly flows through the material and self-heats by Joule heating. This process has potentials for large energy savings due to the reduction in furnace temperatures and shortened sintering time compared to conventional sintering. In addition, the ultra-high heating and cooling rates, along with the impact of electric field and current leads to the formation of unique non-equilibrium features in ceramics, which could greatly enhance their properties. Despite the potential of flash sintering, there are many challenges in moving this technique towards practical applications, such as the microstructure inhomogeneity and lack of understanding of the defects characteristics. In this dissertation, flash sintering was performed on ZnO to investigate the influence of various electrical conditions on the microstructure and defects. Detailed characterization was performed on flash sintered ZnO with and without a controlled current ramp, and contrasting types of current (DC and AC). These parameters show significant impact on the gradient microstructure and defects, and provide a way to tailor the desired characteristics for a wide range of applications. On the other hand, flash sintering of ZnO performed with a high electric field and low current density resulted in the growth of nanostructures. These nanostructures are unique compared to other growth techniques as they contain high density basal-plane stacking faults, and exhibit ultraviolet excitonic emission and red emission at room temperature. The nanostructure growth mechanism was investigated by varying the current density limit and revealed the formation of liquid phases which allowed growth by the vapor-liquid-solid mechanism. These findings present a new exciting route for flash sintering to produce highly defective nanostructures for device applications with new functionalities

Formation of liquid phase and nanostructures in flash sintered ZnO

This study presents the effects of current density limit on flash sintering and the formation of nanostructures in undoped ZnO. The combination of high electric field and low current density (1 and 2 A/cm2) results in the formation of hot spots and fracture as well as ZnO nanostructures in the vicinity of the hot spots. Such phenomena were not observed in the case of higher current density limit of 3 A/cm2. A detailed microscopy analysis revealed that the growth of nanostructures initiated from liquid phase regions at the grain boundaries and within the grain

Ultra-high heating rate effects on the sintering of ceramic nanoparticles: an in situ TEM study

Heating rate plays a major role in the ceramic sintering process, especially in many new advanced sintering techniques. In this study, the effects of ultra-high heating rate up to 1200°C/s have been investigated on various ceramic nanoparticles by in situ transmission electron microscopy (TEM) heating experiments to monitor the morphological changes immediately after the heating process and during the holding time. It was revealed that an ultra-high heating rate is highly effective in densifying 3 mol.% yttria-stabilized zirconia nanoparticles but was less effective for 8 mol.% yttria-stabilized zirconia or zinc oxide due to the competing diffusion mechanisms

Ceramic Material Processing Towards Future Space Habitat: Electric Current-Assisted Sintering of Lunar Regolith Simulant

In situ utilization of available resources in space is necessary for future space habitation. However, direct sintering of the lunar regolith on the Moon as structural and functional components is considered to be challenging due to the sintering conditions. To address this issue, we demonstrate the use of electric current-assisted sintering (ECAS) as a single-step method of compacting and densifying lunar regolith simulant JSC-1A. The sintering temperature and pressure required to achieve a relative density of 97% and microhardness of 6 GPa are 700 °C and 50 MPa, which are significantly lower than for the conventional sintering technique. The sintered samples also demonstrated ferroelectric and ferromagnetic behavior at room temperature. This study presents the feasibility of using ECAS to sinter lunar regolith for future space resource utilization and habitation

The role of point defects and defect gradients in flash sintering of perovskite oxides

The present study investigates the impact of point defects and their redistribution on the flash sintering process. Strontium titanate was chosen as a model system for the group of perovskite ceramics. The characteristics of flash sintering of strontium titanate were analyzed with different acceptor dopant concentrations. The onset of flash sintering was found to be dependent on the acceptor dopant concentration, as expected by the increasing conductivity. A gradient in the microstructure was found after flash sintering with larger grain sizes at the negative electrode. TEM-EDS measurements indicated Ti enrichment at the positive electrode for undoped strontium titanate and strong acceptor segregation for doped strontium titanate. In contrast, grain boundaries at the negative electrode were found to be stoichiometric for the undoped case and the acceptor segregation was less obvious for the doped case

Field-assisted growth of one-dimensional ZnO nanostructures with high defect density

One-dimensional ZnO nanostructures have shown great potential in electronics, optoelectronics and electromechanical devices owing to their unique physical and chemical properties. Most of these nanostructures were grown by equilibrium processes where the defects density is controlled by thermodynamic equilibrium. In this work, flash sintering, a non-equilibrium field-assisted processing method, has been used to synthesize ZnO nanostructures. By applying a high electric field and limiting a low current flow, ZnO nanorods grew uniformly by a vapor-liquid-solid mechanism due to the extreme temperatures achieved near the hot spot. High density basal stacking faults in the nanorods along with ultraviolet excitonic emission and a red emission under room temperature demonstrate the potential of defect engineering in nanostructures via the field-assisted growth method

Nanoscale stacking fault-assisted room temperature plasticity in flash-sintered TiO2.

Ceramic materials have been widely used for structural applications. However, most ceramics have rather limited plasticity at low temperatures and fracture well before the onset of plastic yielding. The brittle nature of ceramics arises from the lack of dislocation activity and the need for high stress to nucleate dislocations. Here, we have investigated the deformability of TiO2 prepared by a flash-sintering technique. Our in situ studies show that the flash-sintered TiO2 can be compressed to ~10% strain under room temperature without noticeable crack formation. The room temperature plasticity in flash-sintered TiO2 is attributed to the formation of nanoscale stacking faults and nanotwins, which may be assisted by the high-density preexisting defects and oxygen vacancies introduced by the flash-sintering process. Distinct deformation behaviors have been observed in flash-sintered TiO2 deformed at different testing temperatures, ranging from room temperature to 600°C. Potential mechanisms that may render ductile ceramic materials are discussed