Microstructure evolution in amorphous Hf-B-Si-C-N high temperature resistant coatings after annealing to 1500 °C in air.

Recently, amorphous Hf-B-Si-C-N coatings found to demonstrate superior high-temperature oxidation resistance. The microstructure evolution of two coatings, Hf7B23Si22C6N40 and Hf6B21Si19C4N47, annealed to 1500 °C in air is investigated to understand their high oxidation resistance. The annealed coatings develop a two-layered structure comprising of the original as-deposited film followed by an oxidized layer. In both films, the oxidized layer possesses the same microstructure with HfO2 nanoparticles dispersed in an amorphous SiOx-based matrix. The bottom layer in the Hf6B21Si19C4N47 coating remains amorphous after annealing while Hf7B23Si22C6N40 recrystallized partially showing a nanocrystalline structure of HfB2 and HfN nanoparticles separated by h-Si3N4 and h-BN boundaries. The HfB2 and HfN nanostructures form a sandwich structure with a HfB2 strip being atomically coherent to HfN skins via (111)-Hf monolayers. In spite of the different bottom layer structure, the oxidized/bottom layer interface of both films was found to exhibit a similar microstructure with a fine distribution of HfO2 nanoparticles surrounded by SiO2 quartz boundaries. The high-temperature oxidation resistance of both films is attributed to the particular evolving microstructure consisting of HfO2 nanoparticles within a dense SiOx-based matrix and quartz SiO2 in front of the oxidized/bottom layer interface acting as a barrier for oxygen and thermal diffusion.

Step terrace tuned anisotropic transport properties of highly epitaxial LaBaCo2O5.5+δ thin films on vicinal SrTiO3 substrates.

Highly epitaxial LaBaCo2O5.5+δ (LBCO) thin films were grown on different miscut (001) SrTiO3 substrates (miscut angle of 0.5°, 3.0°, and 5.0°) to study the substrate surface step terrace effect on the in-plane electrical transport properties. The microstructure studies by X-ray diffraction and transmission electron microscopy indicate that the as-grown films are A-site disordered cubic perovskite structures with the c-axis highly oriented along the film growth direction. The four-probe scanning tunneling microscopy (STM) studies show that the LBCO thin films grown on the vicinal SrTiO3 substrates have a typical semiconductor behavior with the substrate surface terrace step inducing anisotropic electronic transport properties. These results indicate that in highly epitaxial thin films the surface terrace step induced local strains can play an important role in controlling the electronic transport properties and the anisotropic nature.

Interface effects on the electronic transport properties in highly epitaxial LaBaCo2O(5.5+δ) films.

Single-crystalline perovskite LaBaCo2O5.5+δ thin films were grown on a (110) NdGaO3 single-crystal substrate in order to systematically investigate the effect of lattice mismatch on the electrical transport properties in comparison to the films on LaAlO3, SrTiO3, and MgO substrates. Microstructure studies reveal that all of the LaBaCo2O5.5+δ films are of excellent quality with atomically sharp interface structures. The electrical and magnetic transport property studies indicate that the resistivity, magnetoresistance, and magnetic moment of the film are very sensitive to the substrate materials because of the lattice mismatch/interface strain. The Curie temperature, however, is almost independent of the strain imposed by the substrate, probably because of the strong coupling between the nanodomain boundary and interface strain.

The origin of local strain in highly epitaxial oxide thin films.

The ability to control the microstructures and physical properties of hetero-epitaxial functional oxide thin films and artificial structures is a long-sought goal in functional materials research. Normally, only the lattice misfit between the film and the substrate is considered to govern the physical properties of the epitaxial films. In fact, the mismatch of film unit cell arrangement and the Surface-Step-Terrace (SST) dimension of the substrate, named as "SST residual matching", is another key factor that significantly influence the properties of the epitaxial film. The nature of strong local strain induced from both lattice mismatch and the SST residual matching on ferroelectric (Ba,Sr)TiO3 and ferromagnetic (La,Ca)MnO3 thin films are systematically investigated and it is demonstrated that this combined effect has a dramatic impact on the physical properties of highly epitaxial oxide thin films. A giant anomalous magnetoresistance effect (~10(10)) was achieved from the as-designed vicinal surfaces.

Ferroelectric BaTiO3 thin films on Ti substrate fabricated using pulsed-laser deposition.

We report on the fabrication of ferroelectric BaTiO3 thin films on titanium substrates using pulsed laser deposition and their microstructures and properties. Electron microscopy studies reveal that BaTiO3 films are composed of crystalline assemblage of nanopillars with average cross sections from 100 nm to 200 nm. The BaTiO3 films have good interface structures and strong adhesion with respect to Ti substrates by forming a rutile TiO2 intermediate layer with a gradient microstructure. The room temperature ferroelectric polarization measurements show that the as-deposited BTO films possess nearly the same spontaneous polarization as the bulk BTO ceramics indicating formation of ferroelectric domains in the films. Successful fabrication of such ferroelectric films on Ti has significant importance for the development of new applications such as structural health monitoring spanning from aerospace to civil infrastructure. The work can be extended to integrate other ferroelectric oxide films with various promising properties to monitor the structural health of materials.

Tribological behavior of nanocrystalline nickel.

During the last decade, an intensive investigative effort around the globe has been devoted to the understanding of scale effects on materials properties. In spite of their importance, nanoscale effects on tribological properties have attracted little attention. Such effects are of utmost importance to small scale devices such as nano and micro electromechanical systems that contain nanostructured dynamic components that would be difficult to replace or repair. The significant increase in strength arising from the grain size reduction in the nano domain is expected to impact on mechanical processes at asperity contacts that are dominating wear behavior. In the present work, nanocrystalline Ni produced by electroplating was used as a model system to study scale effects on tribological behavior. It was found that compared to bulk (microcrystalline), nanocrystalline Ni can cause a significant reduction in both, the coefficient of friction and wear rate. A consistent relationship was found between grain size, hardness and tribological behavior. It is suggested that the improved tribological behavior of the nanocrystalline Ni is due to the refinement of mechanical processes inhibiting plastic deformation by extensive dislocation motion leading to fracture events.

Ordered, self-organized cobalt nanodots in Co-diamond-like carbon thin films.

A formation process for ordered, self-organized cobalt (Co) nanodots in diamond-like carbon (DLC) thin films deposited by magnetron sputtering in a plasma-assisted Ar/CH4 discharge is presented. episilon-Co dots -5 nm in diameter, separated by 1-2 nm DLC boundaries and arranged in hexagonal arrays were produced on Si substrates. The formation mechanism relies on a self-organization process which is based on surface energy minimization and local magnetic field interaction. The proposed plasma-assisted process presents a controlled and cost-effective bottom-up nanofabrication approach for the production of well-ordered magnetic nanodots based on self-organization.

Effects of solution pH and electrical parameters on hydroxyapatite coatings deposited by a plasma-assisted electrophoresis technique.

Hydroxyapatite (HA) coatings can be deposited using a hybrid process of plasma electrolysis and electrophoresis, called plasma-assisted electrophoretic deposition (PEPD). HA aqueous suspensions with various pH values were prepared using a modified ultrasonic cleaning bath as an agitator/stirrer. Both DC and unbalanced AC power supplies were used to bias the titanium alloy substrate materials employed in this work. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), and Fourier transform infrared spectroscopy (FTIR) were used to observe and analyze coating morphology and microstructure. It was shown that the morphology and composition of the calcium phosphate coatings were significantly influenced by solution pH values; the level of "pure" HA in the coatings' composition corresponded to both solution pH and the type of power supply employed. Loss of hydroxyl radials (i.e., dehydroxylation), which degrades the performance of the hydroxyapatite coating in terms of long-term chemical and mechanical stability, can be virtually eliminated by a combination of high pH and unbalanced AC plasma power. In addition, the underlying TiO2 coatings used to support the HA layer (preproduced by plasma electrolysis process) have a nanoscaled (10-20 nm) polycrystalline structure. TEM studies also revealed a dense, continuous amorphous titania layer (10 nm in thickness) at the interface between the Ti alloy substrate and the TiO2 layer, which may play a role in improving the corrosion resistance of the substrate. Such a nanophase TiO2 layer (if used as a coating alone) may also provide a further improvement in osteoinductive properties, compared to a conventional TiO2 coating on the Ti alloy substrate.

Corrosion of amalgams under sliding wear.

OBJECTIVES: During mastication, dental amalgams are simultaneously subjected to corrosion by the oral environment and to a sliding-wear process by biting forces. In the present study, the effect of sliding wear on the corrosion behavior of two high-copper dental amalgams was investigated. METHODS: An experimental apparatus was utilized that allows electrochemical testing under sliding-wear conditions. Corrosion potential measurements and anodic polarization scans were conducted in 0.1 M NaCl solution under sliding wear to characterize the behavior of two commercial, high-copper, single composition dental amalgams. In addition, long duration tests were conducted to assess possible corrosion and wear synergistic effects. RESULTS: The results showed that sliding wear caused a sharp reduction in the corrosion potential, a significant increase in the corrosion rate and a decrease in the repassivation rate of both amalgams. These effects are due to the mechanical removal by the wear process of the surface protective film formed on dental amalgams. The simultaneous action of sliding wear and corrosion can also induce embrittlement that leads to cracking. SIGNIFICANCE: The present evidence suggests that this cracking may be one of the major contributors to marginal failures of dental amalgam restorations.

New dynamic corrosion test for dental materials.

A new laboratory technique has been developed in an effort to simulate the deterioration processes occurring in dental amalgam restorations while they are exposed to attack by the oral environment and simultaneously subjected to biting forces during mastication. This combined mechanical wear and corrosion action may be one of the major contributors to the degradation of dental amalgam restorations. The technique provides the capability of varying and measuring electrochemical and mechanical parameters during a sliding-wear process in a corrosive environment. A high-copper dental amalgam was selected and tested to demonstrate the applicability of the method in evaluating and studying the effects of the combined action of wear and corrosion processes on dental materials. For the particular amalgam material tested in the present study, it was found that sliding-wear significantly lowered its corrosion potential and increased corrosion rates by at least one order of magnitude.