Troy B. Holland

Direct observation of Lomer-Cottrell Locks during strain hardening in nanocrystalline nickel by in situ TEM

Strain hardening capability is critical for metallic materials to achieve high ductility during plastic deformation. A majority of nanocrystalline metals, however, have inherently low work hardening capability with few exceptions. Interpretations on work hardening mechanisms in nanocrystalline metals are still controversial due to the lack of in situ experimental evidence. Here we report, by using an in situ transmission electron microscope nanoindentation tool, the direct observation of dynamic work hardening event in nanocrystalline nickel. During strain hardening stage, abundant Lomer-Cottrell (L-C) locks formed both within nanograins and against twin boundaries. Two major mechanisms were identified during interactions between L-C locks and twin boundaries. Quantitative nanoindentation experiments recorded show an increase of yield strength from 1.64 to 2.29 GPa during multiple loading-unloading cycles. This study provides both the evidence to explain the roots of work hardening at small length scales and the insight for future design of ductile nanocrystalline metals.

Field assisted sintering of nickel nanoparticles during in situ transmission electron microscopy

This study reports the in situ transmission electron microscopy (TEM) observation of pressure-less field-assisted sintering of agglomerated nanometric nickel particles. Scanning tunneling microscopy inside the TEM was used to apply an electrical current directly to the powder particles. Electrical testing during the experiment reveals that consolidation occurs in the absence of an external heat source. Neck formation between adjacent particles and attendant increase in local Joule heating causes rapid densification. The results represent a first stepping stone towards achieving a fundamental mechanistic understanding of the atomic-scale processes that enable field-enhanced sintering of conductive nanogranular materials.

Crystallization of metallic glasses under the influence of high density dc currents

The effect of a dc current on the crystallization of Vit1A (Zr42.6Ti12.4Cu11.25Ni10Be23.75) and PCNP (Pd40Cu30Ni10P20) metallic glasses was investigated. Samples were isothermally annealed with and without the current, at 623 and 577 K for the two glasses, respectively. Small-angle neutron scattering analyses showed that in the absence of a current, the annealed Vit1A samples were amorphous, but the imposition of a current enhanced the crystallization process, increasing both the size and volume fraction of the crystallites. Similar general observations were seen for the PCNP glass. Differential scanning calorimetry patterns of Vit1A samples indicate a lower thermal stability of samples annealed with a current.

In situ transmission electron microscopy study of dielectric breakdown of surface oxides during electric field-assisted sintering of nickel nanoparticles

The removal of ultra-thin oxide surface layers on nanometric nickel particles is investigated in the framework of electric field-induced dielectric breakdown. In situ transmission electron microscopy was used to directly apply electrical biasing to agglomerates of nanoparticles during simultaneous imaging of the contact area between two adjacent particles. The applied electrical field initiated dielectric breakdown of the surface layers through percolation of oxygen vacancies and the migration of oxygen away from the particle contact, which leads to the formation of metallic necks and their subsequent growth. The experimental results represent direct evidence for surface cleaning effects during electric field-assisted sintering.

Room temperature mechanical behaviour of a Ni-Fe multilayered material with modulated grain size distribution

To gain fundamental insight into the relationship between length scales and mechanical behaviour, Ni-Fe multilayered materials with a 5-μm-layer thickness and a modulated grain size distribution have been synthesized by pulsed electrodeposition. Microstructural studies by SEM and TEM reveal the alternating growth of well-defined layers with either nano (d = 16 nm) or coarse grains (d ≥ 500 nm). Room temperature tensile tests have been performed to investigate the mechanical response and understand the underlying deformation mechanisms. Tensile test results and fractographic studies demonstrate that the overall room temperature mechanical behaviour of the multilayered material, i.e. strength and ductility, is governed primarily by the layers containing nanocrystalline grains. The measured properties have been discussed in the context of modulated grain structure of the multilayered sample and contribution of each grain size regime to the overall strength and ductility.

Metallic superhydrophobic surfaces via thermal sensitization

Superhydrophobic surfaces (i.e., surfaces extremely repellent to water) allow water droplets to bead up and easily roll off from the surface. While a few methods have been developed to fabricate metallic superhydrophobic surfaces, these methods typically involve expensive equipment, environmental hazards, or multi-step processes. In this work, we developed a universal, scalable, solvent-free, one-step methodology based on thermal sensitization to create appropriate surface texture and fabricate metallic superhydrophobic surfaces. To demonstrate the feasibility of our methodology and elucidate the underlying mechanism, we fabricated superhydrophobic surfaces using ferritic (430) and austenitic (316) stainless steels (representative alloys) with roll off angles as low as 4° and 7°, respectively. We envision that our approach will enable the fabrication of superhydrophobic metal alloys for a wide range of civilian and military applications.

High temperature deformability of ductile flash-sintered ceramics via in-situ compression

Flash sintering has attracted significant attention as its remarkably rapid densification process at low sintering furnace temperature leads to the retention of fine grains and enhanced dielectric properties. However, high-temperature mechanical behaviors of flash-sintered ceramics remain poorly understood. Here, we present high-temperature (up to 600 °C) in situ compression studies on flash-sintered yttria-stabilized zirconia (YSZ). Below 400 °C, the YSZ exhibits high ultimate compressive strength exceeding 3.5 GPa and high inelastic strain (~8%) due primarily to phase transformation toughening. At higher temperatures, crack nucleation and propagation are significantly retarded, and prominent plasticity arises mainly from dislocation activity. The high dislocation density induced in flash-sintered ceramics may have general implications for improving the plasticity of sintered ceramic materials.Flash sintering allows for rapid ceramic processing, but the mechanical behavior of such ceramics remains poorly understood. Here, the authors compress micropillars of yttria stabilized zirconia to show flash sintering promotes outstanding plasticity.

Quantitative analysis for in situ sintering of 3% yttria-stablized zirconia in the transmission electron microscope

Studying particle-agglomerate systems compared to two-particle systems elucidates different stages of sintering by monitoring both pores and particles. We report on in situ sintering of 3% yttria-stablized zirconia particle agglomerates in the transmission electron microscope (TEM). Real-time TEM observations indicate neck formation and growth, particle coalescence and pore closure. A MATLAB-based image processing tool was developed to calculate the projected area of the agglomerate with and without internal pores during in situ sintering. We demonstrate the first densification curves generated from sequentially acquired TEM images. The in situ sintering onset temperature was then determined to be at 960 °C. Densification curves illustrated that the agglomerate projected area which excludes the internal observed pores also shrinks during in situ sintering. To overcome the common projection problem for TEM analyses, agglomerate mass-thickness maps were obtained from low energy-loss analysis combined with STEM imaging. The decrease in the projected area was directly related to the increase in mass-thickness of the agglomerate, likely caused by hidden pores existing in the direction of the beam. Access to shrinkage curves through in situ TEM analysis provides a new avenue to investigate fundamental mechanisms of sintering through directly correlating microstructural changes during consolidation with mesoscale densification behavior.

Techniques for Mitigating Thermal Fatigue Degradation, Controlling Efficiency, and Extending Lifetime in a ZnO Thermoelectric Using Grain Size Gradient FGMs

A functionally graded material (FGM) in terms of grain size gradation is fabricated using zinc oxide (ZnO) with spark plasma sintering and an additive manufacturing technique by diffusion bonding layers of material sintered at different temperatures to achieve a thermoelectric generator (TEG) material that can dissipate heat well and retain high energy conversion efficiency for longer-lasting and comparably efficient TEGs. This FGM is compared to a previously made FGM with continuous grain size gradation. Uniform and graded grain size conditions are modeled for thermoelectric output by using thermoelectric properties of the uniform grain size as well as the varying properties seen in the FGMs. The actual thermoelectric output of the samples is measured and compared to the simulations. The grain size has a large effect on the efficiency and efficiency range. The samples are thermally cycled with a fast heating rate to test the thermal stress robustness and degradation, and the resistance at the highest temperature is measured to indicate degradation from thermal stress. The measured efficiency after cycling shows that the FGMs survive longer lifetime than that with uniform small grains.

Field Assisted Sintering Mechanisms

Field assisted sintering studies have produced a wealth of data about the densification behaviors of many powder systems. However, the sheer volume of work has not met with sufficient mechanistic descriptions of the processes in metal or ceramic systems. This fact has, and is, limiting the acceptance and widespread use of this promising technique in larger than laboratory scale manufacturing. We describe here the nature of the influences of electric fields and/or currents, changes in heating rate, and the effects of applied pressures upon ceramic and metal systems in context of the commonly accepted stages of sintering. As many of the specific mechanisms discussed have not been directly characterized within field assisted sintering studies we focus on the established theoretical underpinnings to better understand their influence and to enable definitive future experimentation on this area of research.