Probing the Gold/Water Interface with Surface-Specific Spectroscopy.

Water is an integral component in electrochemistry, in the generation of the electric double layer, and in the propagation of the interfacial electric fields into the solution; however, probing the molecular-level structure of interfacial water near functioning electrode surfaces remains challenging. Due to the surface-specificity, sum-frequency-generation (SFG) spectroscopy offers an opportunity to investigate the structure of water near working electrochemical interfaces but probing the hydrogen-bonded structure of water at this buried electrode-electrolyte interface was thought to be impossible. Propagating the laser beams through the solvent leads to a large attenuation of the infrared light due to the absorption of water, and interrogating the interface by sending the laser beams through the electrode normally obscures the SFG spectra due to the large nonlinear response of conduction band electrons. Here, we show that the latter limitation is removed when the gold layer is thin. To demonstrate this, we prepared Au gradient films on CaF2 with a thickness between 0 and 8 nm. SFG spectra of the Au gradient films in contact with H2O and D2O demonstrate that resonant water SFG spectra can be obtained using Au films with a thickness of ∼2 nm or less. The measured spectra are distinctively different from the frequency-dependent Fresnel factors of the interface, suggesting that the features we observe in the OH stretching region indeed do not arise from the nonresonant response of the Au films. With the newfound ability to probe interfacial solvent structure at electrode/aqueous interfaces, we hope to provide insights into more efficient electrolyte composition and electrode design.

Experimental and Theoretical Investigation on Phase Formation and Mechanical Properties in Cr-Co-Ni Alloys Processed Using a Novel Thin-Film Quenching Technique.

The Cr-Co-Ni system was studied by combining experimental and computational methods to investigate phase stability and mechanical properties. Thin-film materials libraries were prepared and quenched from high temperatures up to 700 °C using a novel quenching technique. It could be shown that a wide A1 solid solution region exists in the Cr-Co-Ni system. To validate the results obtained using thin-film materials libraries, bulk samples of selected compositions were prepared by arc melting, and the experimental data were additionally compared to results from DFT calculations. The computational results are in good agreement with the measured lattice parameters and elastic moduli. The lattice parameters increase with the addition of Co and Cr, with a more pronounced effect for the latter. The addition of ∼20 atom % Cr results in a similar hardening effect to that of the addition of ∼40 atom % Co.

Combinatorial Study on Phase Formation and Oxidation in the Thin Film Superalloy Subsystems Co-Al-Cr and Co-Al-Cr-W.

Two Co-based superalloy subsystems, the ternary system Co-Al-Cr and the quasi-ternary system Co-Al-Cr-W with a constant amount of 10 at. % W, were deposited as thin-film materials libraries and analyzed in terms of phase formation and oxidation behavior at 500 °C in air. By combining energy-dispersive X-ray analysis and X-ray photoelectron spectroscopy high-throughput composition measurements, a detailed evaluation of the dependence between the initial multinary metal composition and the oxide scale composition which is forming upon oxidation on the surface of the thin film is established. Phase maps for both materials libraries are provided by high-throughput X-ray diffraction. In addition, the oxidation of a Co-Al-Cr-W bulk sample was analyzed and compared to a corresponding film in the library.

High-Throughput Structural and Functional Characterization of the Thin Film Materials System Ni-Co-Al.

High-throughput methods were used to investigate a Ni-Co-Al thin film materials library, which is of interest for structural and functional applications (superalloys, shape memory alloys). X-ray diffraction (XRD) measurements were performed to identify the phase regions of the Ni-Co-Al system in its state after annealing at 600 °C. Optical, electrical, and magneto-optical measurements were performed to map functional properties and confirm XRD results. All results and literature data were used to propose a ternary thin film phase diagram of the Ni-Co-Al thin film system.

Phase Formation and Oxidation Behavior at 500 °C in a Ni-Co-Al Thin-Film Materials Library.

The complete ternary system Ni-Co-Al was fabricated as a thin film materials library by combinatorial magnetron sputtering and was annealed subsequently in several steps in Ar and under atmospheric conditions at 500 °C. Ni-Co-Al is the base system for both Ni- and Co-based superalloys. Therefore, the phases occurring in this system and their oxidation behavior is of high interest. The Ni-Co-Al materials library was investigated using high-throughput characterization methods such as optical measurements, resistance screening, automated EDX, automated XRD, and XPS. From the obtained data a thin film phase diagram for the Ni-Co-Al system in its state after annealing at 500 °C in air was established. Furthermore, a surface oxide composition map of the full Ni-Co-Al system for oxidation at 500 °C was concluded. As a result, it could be shown that at 500 °C an amount of 10 at. % Al is necessary for a Ni-Co-Al thin film to produce a protective Al-oxide scale.