Synthesis and Microstructure of BaCO3 and BaTiO3 coatings produced on titanium by plasma electrolytic oxidation

Significance 

Barium carbonate (BaCo3) is a thermodynamically stable heavy metal carbonate with many applications in producing glass, ceramic and ferroelectric materials. The material has demonstrated strong potential applications in catalysis, sensors, solid oxide fuel cells and batteries. Alternatively, Barium titanate (BaTiO3) present a ferroelectric material with remarkable properties such as high dielectric constant, good ferroelectric properties, large electro-optic and non-linear optic coefficients. It is well known that titanium and its alloys have a unique combination of high strength to weight ratio, excellent biocompatibility and high corrosion resistance, and are widely used in many industries such as aerospace, marine and biomedical. Therefore, combining functional BaCO3 and BaTiO3 nanostructures and Ti is expected to achieve new engineered functional materials by integrating their desirable properties. For instance, ferroelectric BaTiO3 films fabricated on structural materials (titanium, nickel, etc.) using pulsed laser deposition (PLD) can be used for structural health monitoring.

Researchers previously fabricated barium carbonate using various approaches and managed to produce barium titanate by simply heating TiO2-coated BaCO3 particles and by solid-state reaction between BaCO3 and TiO2. Nonetheless, a more feasible approach of producing the two is still required. To this end, Engineer Hsiao-Chien Wu, Professor Jiechao Jiang and distinguished university Professor Efstathios I. Meletis from the Department of Materials Science and Engineering at University of Texas at Arlington developed a new fabrication technique for BaCO3 and BaTiO3 nanostructure coatings on titanium using plasma electrolytic oxidation processing method. Their work is currently published in the research journal, Applied Surface Science.

In their approach, barium carbonate and barium titanate layers were coated on titanium by plasma electrolytic oxidation at 5 mA/cm2 in 0.5M Ba (CH3COO)2 and 2M sodium hydroxide electrolyte. The research team then carefully looked at the coatings characteristics using a variety of advanced techniques including scanning electron microscopy, X-ray and electron diffraction, and high-resolution transmission electron microscopy.

The authors found that processing for 1h required low voltages and yielded a BaCO3 coating along with a thin TiO2 interlayer (~60 nm). The coating was observed to be composed of orthorhombic BaCO3 nanorods that were vertically oriented at the bottom layer close to Ti substrate and horizontally oriented in the top layer close to the surface. Further, the team reported that processing for 4h required higher voltages resulting in generation of microarc discharges and discharge channel formation. These conditions produced a tetragonal BaTiO3 coating along with a broader TiO2 interlayer at the Ti interface composed of rutile and brookite nanostructures.

In summary, Professor Efstathios Meletis and his colleagues exploited the innovation of using plasma electrolytic oxidation technique to produce either barium carbonate or barium titanate layers on titanium. Results obtained showed that the BaTiO3 was produced by transformation of pre-existing BaCO3 layer. Further, the BaCO3 to BaTiO3 transformation was found to be facilitated by their epitaxial relationship. Overall, based on their findings, the Texas University research team proposed a structural model to elegantly describe the BaTiO3 growth from the BaCO3 lattice.

About the author

Hsiao-Chien Wu received his master degree in Materials Science and Engineering at the University of Texas at Arlington, Texas, in 2017. He is currently an Application Engineer in HMI-ASML, ASML Holding Semiconductor Company, Veldhoven, Netherlands.

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About the author

Jiechao Jiang received his PhD degree in materials physics from the University of Science and Technology Beijing, China, in 1993. He is currently a professor of research in the department of materials science and engineering and the facility manager of the Characterization Center for Materials and Biology at the University of Texas at Arlington, Texas, USA.

His research interest includes materials characterization using AFM, TEM (analytical, high resolution & in-situ), SEM, XRD, Auger/XPS, and thermal analysis (TGA/DSC); microstructures and defects of advanced functional materials and minerals, atomic structure modeling for new phases, multi-layers and interfaces; self-assembled nanostructures for nano-electronic and opto-electric devices and nano fuel cells; processing, microstructures, and property relationships in micro/nano-scale materials; nucleation, growth mechanisms, interfaces and surface of epitaxial and multifunctional coatings.

About the author

Efstathios “Stathis” I. Meletis received his Diploma in Chemical Engineering from the National Technical University of Athens, Greece and his M.Sc. and Ph.D. in Materials Science & Engineering (MSE) from Georgia Institute of Technology, USA. He held appointments at Georgia Tech, IIT Research Institute, University of California, Davis and Louisiana State University where he was an Endowed Professor. He currently is a Distinguished University Professor and Chair of MSE at the University of Texas, Arlington.

His major research contributions are in the areas of surface engineering, multifunctional thin films, small-scale materials, and material-environment interactions. He has invented novel intensified plasma treatments for surface hardening and producing functionally gradient surface layers. In the area of nanomaterials, his group was the first to achieve self-assembling of perovskite-type oxides and metal/ceramic nanocomposite thin films with high aspect ratio.

His recent work focuses on high temperature coatings for extreme environments, surface engineering by plasma processes and scale effects on material properties. His research program has been funded from NSF, NASA, ARO, DARPA, and other federal and industrial sources. Dr. Meletis has been a recipient of the William Fulbright Scholar Award and is the Editor-in-Chief of the Journal of Nano Research.

Reference

Hsiao-Chien Wu, Jiechao Jiang, Efstathios I. Meletis. Microstructure of BaCO3 and BaTiO3 coatings produced on titanium by plasma electrolytic oxidation. Applied Surface Science, volume 506 (2020) 144858.

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