Hannes Rijckaert

Amino Acid-Based Stabilization of Oxide Nanocrystals in Polar Media: From Insight in Ligand Exchange to Solution 1H NMR Probing of Short-Chained Adsorbates

Ligand exchange is a crucial step between nanocrystal synthesis and nanocrystal application. Although colloidal stability and ligand exchange in nonpolar media are readily established, the exchange of native, hydrophobic ligands with polar ligands is less systematic. In this paper, we present a versatile ligand exchange strategy for the phase transfer of carboxylic acid capped HfO2 and ZrO2 nanocrystals to various polar solvents, based on small amino acids as the incoming ligand. To gain insight in the fundamental mechanism of the exchange, we study this system with a combination of FTIR, zeta potential measurements, and solution (1)H NMR techniques. The detection of surface-associated, small ligands with solution NMR proves challenging in this respect. Tightly bound amino acids are undetectable, but their existence can be proven through displacement with other ligands in titration experiments. Alternatively, we find that methyl moieties belonging to bound species can circumvent these limitations because of their more favorable relaxation properties as a result of internal mobility. As such, our results are not limited to amino acids but to any short-chained ligand and will therefore facilitate the rigorous investigation and understanding of various ligand exchange processes.

Enhanced flux pinning in YBCO multilayer films with BCO nanodots and segmented BZO nanorods

The flux pinning properties of the high temperature superconductor YBa2Cu3O7−δ (YBCO) have been conventionally improved by creating both columnar and dot-like pinning centres into the YBCO matrix. To study the effects of differently doped multilayer structures on pinning, several samples consisting of a multiple number of individually BaZrO3 (BZO) and BaCeO3 (BCO) doped YBCO layers were fabricated. In the YBCO matrix, BZO forms columnar and BCO dot-like defects. The multilayer structure improves pinning capability throughout the whole angular range, giving rise to a high critical current density, Jc. However, the BZO doped monolayer reference still has the most isotropic Jc. Even though BZO forms nanorods, in this work the samples with multiple thin layers do not exhibit a c axis peak in the angular dependence of Jc. The angular dependencies and the approximately correct magnitude of Jc were also verified using a molecular dynamics simulation.

Chemical solution deposition of functional ceramic coatings using ink-jet printing

Abstract This paper discusses the development of environmentally-friendly precursor inks suited for ink-jet printing of functional ceramic coatings. We synthesized superconducting materials, SrTiO3 thin films for coated conductor applications and transparent TiO2 photocatalytic coatings. Here, we discuss all aspects of ink formulation, including the stabilization of metal ions, nanoparticle inks or combination of both. This demands the investigation and determination of the inks rheological parameters. Ceramic nanoparticles are often incorporated in our inks to decrease thermal processing temperatures (e.g., TiO2 or YSZ coatings...) or enhance the properties of the functional ceramic coating (e.g., pinning centres in superconducting coatings). These ceramic nanoparticles (ZrO2, HfO2, TiO2...) are synthesized through methods based on microwave heating from aqueous and/or organic solutions. With that, we aim at developing smart and environmentally friendly processes that require lower energy input.

Thickness characterization toolbox for transparent protective coatings on polymer substrates

The thickness characterization of transparent protective coatings on functional, transparent materials is often problematic. In this paper, a toolbox to determine the thicknesses of a transparent coating on functional window films is presented. The toolbox consists of a combination of secondary ion mass spectrometry and profilometry and can be transferred to other transparent polymeric materials. A coating was deposited on designed model samples, which were characterized with cross-sectional views in transmission and in scanning/transmission electron microscopy and ellipsometry. The toolbox was then used to assess the thicknesses of the protective coatings on the pilot-scale window films. This coating was synthesized using straightforward sol-gel alkoxide chemistry. The kinetics of the condensation are studied in order to obtain a precursor that allows fast drying and complete condensation after simple heat treatment. The shelf life of this precursor solution was investigated in order to verify its accordance to industrial requirements. Deposition was performed successfully at low temperatures below 100 °C, which makes deposition on polymeric foils possible. By using roll-to-roll coating, the findings of this paper are easily transferrable to industrial scale. The coating was tested for scratch resistance and adhesion. Values for the emissivity (ε) of the films were recorded to justify the use of the films obtained as infrared reflective window films. In this work, it is shown that the toolbox measures similar thicknesses to those measured by electron microscopy and can be used to set a required thickness for protective coatings.

Pair Distribution Function Analysis of ZrO2 Nanocrystals and Insights in the Formation of ZrO2-YBa2Cu3O7 Nanocomposites

The formation of superconducting nanocomposites from preformed nanocrystals is still not well understood. Here, we examine the case of ZrO2 nanocrystals in a YBa2Cu3O7−x matrix. First we analyzed the preformed ZrO2 nanocrystals via atomic pair distribution function analysis and found that the nanocrystals have a distorted tetragonal crystal structure. Second, we investigated the influence of various surface ligands attached to the ZrO2 nanocrystals on the distribution of metal ions in the pyrolyzed matrix via secondary ion mass spectroscopy technique. The choice of stabilizing ligand is crucial in order to obtain good superconducting nanocomposite films with vortex pinning. Short, carboxylate based ligands lead to poor superconducting properties due to the inhomogeneity of metal content in the pyrolyzed matrix. Counter-intuitively, a phosphonate ligand with long chains does not disturb the growth of YBa2Cu3O7−x. Even more surprisingly, bisphosphonate polymeric ligands provide good colloidal stability in solution but do not prevent coagulation in the final film, resulting in poor pinning. These results thus shed light on the various stages of the superconducting nanocomposite formation.