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At least 379 records · Page 21

Enhancing catalytic activity of rhodium towards methanol electro-oxidation in both acidic and alkaline media by alloying with iron

The methanol electrooxidation catalysts in the form of Rh and FeRh thin films were prepared by magnetron sputtering deposition. To activate the FeRh catalyst, the as-prepared FeRh films were cycled in 0.1 M HClO 4 electrolyte in potential window from -0.25 V to 0.8 V (vs. Ag/AgCl). The dissolution of Fe atoms during the cycling leads to the formation of Rh-skeleton surface. Obtained FeRh catalysts exhibit significantly enhanced activity to methanol electrooxidation in both acidic and alkaline environments comparing to pure Rh catalyst. The optimal concentration of Fe is found to be 50%. Electrochemical impedance spectroscopy investigations show the higher rate of methanol dehydrogenation as well as better tolerance to CO intermediates poisoning of the FeRh catalysts. Furthermore, this study demonstrates that Rh-based catalysts can be considered as alternative to Pt-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combinatorial Synthesis and High-Throughput Characterization of Microstructure and Phase Transformation in Ni–Ti–Cu–V Quaternary Thin-Film Library

Ni–Ti–based shape memory alloys (SMAs) have found widespread use in the last 70 years, but improving their functional stability remains a key quest for more robust and advanced applications. Named for their ability to retain their processed shape as a result of a reversible martensitic transformation, SMAs are highly sensitive to compositional variations. Alloying with ternary and quaternary elements to fine-tune the lattice parameters and the thermal hysteresis of an SMA, therefore, becomes a challenge in materials exploration. Combinatorial materials science allows streamlining of the synthesis process and data management from multiple characterization techniques. In this study, a composition spread of Ni–Ti–Cu–V thin-film library was synthesized by magnetron co-sputtering on a thermally oxidized Si wafer. Composition-dependent phase transformation temperature and microstructure were investigated and determined using high-throughput wavelength dispersive spectroscopy, synchrotron X-ray diffraction, and temperature-dependent resistance measurements. Of the 177 compositions in the materials library, 32 were observed to have shape memory effect, of which five had zero or near-zero thermal hysteresis. These compositions provide flexibility in the operating temperature regimes that they can be used in. A phase map for the quaternary system and correlations of functional properties are discussed with respect to the local microstructure and composition of the thin-film library.

42 ENGINEERING↗

High-throughput characterization of Ag–V–O nanostructured thin-film materials libraries for photoelectrochemical solar water splitting

Ag–V–O thin-film materials libraries, with both composition (Ag 22-77 V 23-78 O x ) and thickness (123–714 nm) gradients were fabricated using combinatorial reactive magnetron co-sputtering aiming on establishing relations between composition, structure, and functional properties. As-deposited libraries were annealed in air at 300 °C for 10 h. High-throughput characterization methods of composition, structure and functional properties were used to identify photoelectrochemically active regions. The phases AgV 6 O 15 , Ag 2 V 4 O 11 , AgVO 3 , and Ag 4 V 2 O 7 were observed throughout the composition gradient. The photoelectrochemical properties of Ag–V–O films are dependent on composition and morphology. An enhanced photocurrent density (~300–554 μA/cm 2 ) was obtained at 30 to 45 at.% Ag along the thickness gradient. Thin films of these compositions show a nanowire morphology, which is an important factor for the enhancement of photoelectrochemical performance. The photoelectrochemically active regions were further investigated by high-throughput synchrotron-X-ray diffraction and transmission electron microscopy (Ag 32 V 68 O x ) which confirmed the presence of Ag 2 V 4 O 11 as the dominating phase along with the minor phases AgV 6 O 15 and AgVO 3 . This enhanced photoactive region shows bandgap values of ~2.30 eV for the direct and ~1.87 eV for the indirect bandgap energies. Finally, the porous nanostructured films improve charge transport and are hence of interest for photoelectrochemical water splitting.

36 MATERIALS SCIENCE↗

Corrosion resistance of functionally graded TiN/Ti coatings for proton exchange membrane fuel cells

Bipolar Plates (BPP) are important components of proton exchange membrane fuel cell (PEMFC) stacks. In the development of innovative fuel cell designs, it is advantageous to use aluminum for these applications, however, this material lacks the necessary corrosion resistance. Since the performance of PEMFC stacks depends on BPP properties, in particular, corrosion resistance, depositing titanium nitride (TiN) thin films onto aluminum substrates may improve their efficiency and durability. Present work focuses on improving corrosion resistance and hydrophobicity of TiN/Ti by using N graded films deposited onto aluminum substrates (AA-1100) by grid-assisted magnetron sputtering (GAMS). Electrochemical impedance spectroscopy (EIS) with potentiodynamic and potentiostatic polarization are used to investigate the performance of the substrate/film system at room temperature and 70 oC, thus simulating a prototypic PEMFC electrolyte environment. Electrochemical test results showed that graded TiN films improved corrosion resistance when compared with both the homogeneous films and the AA1100 uncoated substrate. Furthermore, contact angle results reveal improved hydrophobicity for both homogeneous and graded TiN coatings when compared with the AA1100 substrate.

25 ENERGY STORAGE↗

Structural dependence of hydrogen evolution reaction on transition metal catalysts sputtered at different temperatures in alkaline media

In the present article, we studied the catalytic activity of magnetron sputtered Mo, V, Ni, and Co thin films for hydrogen evolution reaction (HER) in the alkaline electrolyte. Here, we find that the HER potentials (η 10 ) of the Mo and V thin film catalysts sputtered at 800 °C shift positive with respect to those of the film catalysts sputtered at 25°C. For Mo metal the observed shift of η 10 was 280 mV and for V metal observed shift of η 10 was 390 mV. On the other hand, minimal effect of sputtering temperature on both Ni and Co thin film catalyst activity for HER was observed. Structural analysis reveals that Mo and V prepared at 800 °C have uncommon face centered cubic (fcc, 0.74 packing density) structure as opposed to room-temperature sputtered Mo and V thin films which have common body centered cubic (bcc, 0.68 packing density) structure, resulting in significant increases of the packing densities when they are prepared at 800 °C. On the other hand, the high-temperature prepared thin films of Ni and Co retained fcc structures, resulting in no density changes compared to the room-temperature prepared fcc Ni and hexagonal close packed (hcp, 0.74 packing density) Co. Impedance spectroscopy shows that fcc Mo is a better catalyst than fcc Ni, which is considered an industry standard for non-noble pure metal-based catalysts in alkaline media. Stability tests also suggest that fcc Mo thin film catalysts prepared at 800 °C are more durable than fcc Ni thin films. Our study points out that structure phases of catalysts can be a key factor governing the activities of transition metals for HER in alkaline media.

08 HYDROGEN↗

10% Efficiency Cu(In,Ga)Se2 Solar Cell with Strongly (220)/(204) Oriented Cu-Poor Absorber Layers Sputtered Using Single Quaternary Target

Cu-poor CIGS thin films were fabricated by RF magnetron sputtering from a single quaternary target with the composition of Cu0.7In0.7Ga0.3Se2, in an effort to improve the cell efficiency of CIGS solar cells. The Cu-poor thin films with the ([Cu]/[In]+[Ga]) composition ratios of 0.70-0.77 were obtained showing that the composition of the target can be transferred to the film. It was also observed that the strongly (220)/(204) preferred orientation appeared at the substrate temperatures higher than 600 degrees C, which is known to be essential for achieving high-quality CIGS solar cells. This result indicates that the Cu-Se compounds present in trace amounts of CIGS films hinder the (112) orientation and promotes the growth of the (220) orientation. As a result, the CIGS absorber layer with the Cu-poor composition and the (220)/(204) preferred orientation exhibited a drastically improved cell efficiency of 10.02%.

14 SOLAR ENERGY↗

Synthesis of bulk reactive Ni–Al composites using high pressure torsion

Self-propagating exothermic reactions, for instance in the nickel-aluminum (Ni-Al) system, have been widely studied to create high performance intermetallic compounds or for in-situ welding. Their easy ignition once the phase spacing is reduced below the micron scale, makes top-down methods like high-energy ball milling, ideal to fabricate such reactive nanostructures. A major drawback of ball milling is the need of a sintering step to form bulk pieces of the reactive material. However, this is not possible, as the targeted reactions would already proceed. Therefore, we investigate the ability of high pressure torsion as an alternative process, capable to produce bulk nanocomposites from powder mixtures. Severe straining of powder mixtures with a composition of 50 wt% Ni and 50 wt% Al enables fabrication of self-reactive bulk samples with microstructures similar to those obtained from ball milling or magnetron sputtering. Additionally, samples deformed at ambient temperature are highly reactive and can be ignited significantly below the Al melting point, finally predominantly consisting of Al 3 Ni 2 and Al 3 Ni, independent of the applied strain. Although the reaction proceeds first at the edge of the disk, the strain gradient present in the disks does not prevent reaction of the whole sample.

36 MATERIALS SCIENCE↗

Steam oxidation of chromium corrosion barrier coatings for sic-based accident tolerant fuel cladding

SiC-based materials are currently being considered for accident tolerant fuel (ATF) cladding, however, there are concerns regarding hydrothermal corrosion rates and hermeticity. These issues may be addressed with the utilization of a Cr corrosion barrier coating (CBC) but the interaction of Cr with SiC under loss of coolant accident (LOCA) conditions needs to be investigated. In the present work, Cr coatings were deposited onto chemically vapor deposited (CVD) SiC with either high power impulse magnetron sputtering (HiPIMS), cathodic arc (CA), or a combination of both. Annealing and steam thermogravimetric analysis (TGA) was used to study reaction product formation with and without oxidation. Additionally, after 1200 °C annealing, formation of a Cr x C y carbide layer at the ambient interface and a Cr x Si y C z silicide layer at the SiC interface was observed. After 1200 °C TGA exposure, similar carbide and silicide layers were observed but with a Cr 2 O 3 outer reaction layer and a Si and O rich interfacial layer forming between the carbide and silicide layers. Initial mass gain of the coatings during the 1200 °C TGA exposure was parabolic and were similar to reported rates of chromia formation. Mass gain behavior and observed transitions in chromia microstructure indicate that metallic Cr may be consumed within the first ~1 h at 1200 °C and that subsequent chromia formation occurs at the expense of the underlying Cr carbide layer. Overall, the results show no detrimental impact of Cr coatings on the steam oxidation resistance of SiC up to 4 h at 1200 °C.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The response of accident tolerant fuel cladding to LOCA burst testing: A comparative study of leading concepts

Accident tolerant fuel claddings seek to improve safety margins during loss-of-coolant accident (LOCA) scenarios by reducing cladding steam oxidation rates, hydrogen production, delaying or mitigating cladding burst, and reducing cladding deformation. After rapid and extensive progress in recent years, Cr coated Zr-based alloys, ferritic FeCrAl, and SiC/SiC ceramic matrix composites (CMCs) have emerged as the most promising cladding concepts, but there are few studies comparing the accident tolerance of all three concepts simultaneously. Here, in this study, LOCA burst testing has been conducted on Cr high impulse power magnetron sputtered Zry-4 (Cr/Zry-4), C26M (FeCrAl), and SiC/SiC SiGA (CMC). Experimental observations indicate Cr/Zry-4 burst at higher temperatures than Zry-4 however the effectiveness of the coating on mitigating ZrO 2 formation via Cr 2 O 3 formation depended on physical proximity to the burst opening. No dramatic improvement in diametrical strain nor opening geometry was observed. C26M burst at higher temperatures than Zry-4 at lower pressures, exhibiting small amounts of strain and smaller openings, and formed slow-growing Al 2 O 3 regardless of location. The CMCs did not burst or show any macroscopic signs of deformation, all the way up to an internal cladding pressure of 15.2 MPa. High temperature expanding Nb plug testing indicated that CMC room temperature strength may persist up to 1650°C, with an approximately 40% loss of strength at 1900°C. CMC steam oxidation was also compared to reference chemically vapor deposited SiC up to 1700°C, and CMCs were found to oxidize at slightly accelerated rates that were still orders of magnitude lower than bare Zry-4. Projected H 2 generation during LOCA burst testing showed that when accounting for cladding burst exposing inner diameters to steam, Cr coated Zry-4 reduced H 2 generation by a factor of two compared with bare Zry-4, while both C26M and SiC/SiC reduced H 2 generation by orders of magnitude relative to bare Zry-4.

36 MATERIALS SCIENCE↗

Investigation of W-SiC compositionally graded films as a divertor material

W-SiC composite material is a promising plasma-facing material candidate alternative to pure W due to the low neutron activation, low impurity radiation, and low tritium diffusivity of SiC while leveraging the high erosion resistance of the W armor. Additionally, W and SiC have high thermomechanical compatibility given their similar thermal expansion rates. The present study addresses the synthesis and performance of compositionally graded W-SiC films fabricated by pulsed-DC magnetron sputtering. Compositional gradients were characterized using transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS), and crystallographic information was obtained using electron diffraction and X-ray diffraction (XRD). Samples were exposed to L-mode deuterium plasma discharges in the DIII-D tokamak using the Divertor Material Evaluation System (DiMES). Post-mortem characterizations were performed using scanning electron microscopy (SEM) and XRD. Electron diffraction and XRD showed that the compositionally graded W-SiC films were composed of polycrystalline W and amorphous SiC with amorphous W+SiC interlayers. No macroscopic delamination or microstructural changes were observed under mild exposure conditions. Here, this study serves as a preliminary examination of W-SiC compositionally graded composites as a potential candidate divertor material in future tokamak devices.

36 MATERIALS SCIENCE↗

Electron doping of NdNiO 3 thin films using dual chamber CaH 2 annealing

Hydrogen donor doping has been exploited as a strategy to manipulate the electronic structure and electrical properties of functional oxide systems. Especially, the development of synthetic methods to achieve electron doping of perovskite rare-earth nickelate thin films utilizing interstitial hydrogen is highly desirable considering the rich electronic phase diagram hosting several functional properties. Here, in this work, we present the hydrogenation of NdNiO 3 (NNO) thin films using CaH 2 annealing and the resulting giant modulation of electrical resistivity in hydrogenated NNO (H–NNO) thin films. Magnetron sputtering was employed to deposit epitaxial ~60 nm-thin NNO films on single crystal LaAlO 3 (LAO) substrates. The formation of the pristine perovskite NNO phase was realized after annealing the films at 500 °C for 24 h. CaH 2 annealing of NNO thin films for time durations ranging from 1 to 6 h was performed in a vacuumed ampule with two interconnected chambers at 280 °C. The two-chamber design enables a simple and clean approach for hydrogen doping without physical contact between the powder and sample of interest. X-ray diffraction and Raman spectroscopy revealed the formation of NNO in pristine samples, and the subsequent hydrogen incorporation upon CaH 2 annealing without forming any impurity phases. The conversion of the oxidation state of Ni towards +2 upon CaH 2 annealing was probed using X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. Consequently, a substantial increase in the room-temperature resistivity was observed upon CaH 2 annealing indicating the formation of a strongly correlated electronic configuration of Ni in H–NNO due to electron doping. Overall, the findings of this study highlight the versatility of CaH 2 annealing as an electron doping method to tune the electrical properties of correlated oxides at low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Wettability, structural and optical properties investigation of TiO{sub 2} nanotubular arrays

Graphical abstract: FESEM images of the TiO 2 nanotube layers formed at 0.5 wt% NH4F/ glycerol. - Highlights: • Structural property investigation of TiO{sub 2} nanotube. • Evaluation of wettability of TiO{sub 2} nanotube. • Study on optical properties of TiO{sub 2} nanotube. • The effect of anatase phase on optical and wettability properties of TiO{sub 2.} - Abstract: In this study, the effect of microstructural evolution of TiO{sub 2} nanotubular arrays on wettability and optical properties was investigated. Pure titanium was deposited on silica glass by PVD magnetron sputtering technique. The Ti coated substrates were anodized in an electrolyte containing NH{sub 4}F/glycerol. The structures of the ordered anodic TiO{sub 2} nanotubes (ATNs) as long as 175 nm were studied using field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD). The result shows a sharp peak in the optical absorbance spectra around the band gap energy, 3.49–3.42 eV for annealed and non-annealed respectively. The thermal process induced growth of the grain size, which influence on the density of particles and the index of refraction. Furthermore, the wettability tests' result displays that the contact angle of intact substrate (θ = 74.7°) was decreased to 31.4° and 17.4° after anodization for amorphous and heat treated (450 °C) ANTs coated substrate, respectively.

36 MATERIALS SCIENCE↗

Ti{sub 2}AlN thin films synthesized by annealing of (Ti+Al)/AlN multilayers

Highlights: • Epitaxial thin films of the MAX phase Ti{sub 2}AlN are obtained by thermal annealing. • A new metastable (Ti,Al,N) solid solution with the structure of α-T is evidenced. • The formation of the MAX phase occurs at low temperature (600 °C). - Abstract: Single-phase Ti{sub 2}AlN thin films were obtained by annealing in vacuum of (Ti + Al)/AlN multilayers deposited at room temperature by magnetron sputtering onto single-crystalline (0001) 4H-SiC and (0001) Al{sub 2}O{sub 3} substrates. In-situ X-ray diffraction experiments combined with ex-situ cross-sectional transmission electron microscopy observations reveal that interdiffusion processes occur in the multilayer at a temperature of ∼400 °C leading to the formation of a (Ti, Al, N) solid solution, having the hexagonal structure of α-Ti, whereas the formation of Ti{sub 2}AlN occurs at 550–600 °C. Highly oriented (0002) Ti{sub 2}AlN thin films can be obtained after an annealing at 750 °C.

36 MATERIALS SCIENCE↗

Improved stability of aluminum co-sputtered indium zinc oxide thin-film transistor

Highlights: • We fabricated AOS TFTs using Al co-sputtered IZO thin films as active layers. • Low Al ratio in IZO thin films suppresses carrier concentration and oxygen vacancies. • Addition of 0.62 wt.% Al into IZO could reduce the chance of creating trap states. • Fabricated Al-IZO TFT has improved bias stability under bias stress conditions. • Optical transmittance of Al-IZO film greater than 90% in visible light (400–800 nm). - Abstract: The electrical performance and bias stability of radio-frequency magnetron co-sputtered aluminum-indium-zinc oxide (Al-IZO) thin-film transistors (TFTs) were investigated, with respect to the atomic proportions of Al. Other parameters such as the indium-zinc oxide (IZO) target power, oxygen partial pressure, and initial and process pressures of the chamber were fixed. At a low Al atomic ratio (0.62 wt.%), the electrical performance and bias stability of the Al-IZO TFT were optimized because of the suppression of the generation of oxygen vacancies and the strong bond between Al and oxygen atoms (Al–O; 501.9 kJ/mol). Compared to pure IZO TFTs, the Al-IZO TFT exhibited a small shift in the threshold voltage under bias stress conditions. A higher threshold voltage of −2.24 V and an improved subthreshold swing of 1.35 V/dec were also observed. We demonstrated that the Al-IZO TFT could be a promising candidate for switching and driving operations in mass-produced display applications.

36 MATERIALS SCIENCE↗

Investigation of CrMnV and CrMnTiV multi principal element alloys thin films for use as exit windows of electron beam accelerators

Here, this study explores CrMnV and CrMnTiV multi principal element alloy (MPEA) films as candidates for electron beam exit windows in industrial, high-power accelerators. Films were deposited via magnetron sputtering on various substrates and exposed to 66 kGy of 10 MeV e-beam irradiation. Structural and mechanical properties were analyzed using FESEM, XRD, and nanoindentation. CrMnTiV films exhibited superior grain uniformity and hardness, regardless of the substrate type. Compared to bulk materials, both MPEA films demonstrated higher hardness and excellent radiation resistance. These results highlight the potential of MPEA films as durable, radiation-tolerant materials for high-performance accelerator exit window applications.

Electron Beam Irradiation↗

Cost-efficiency enhancement of X- and Ku-band split waveguides for industrial accelerators

Compact microwave electron linear accelerators must operate at high frequencies in order to maintain tight SWaP (size, weight, and power) requirements, set by modern applications. Currently, the frequencies are practically limited to X- and Ku-bands because of the availability of MW-class magnetrons, required to achieve beam energies of several MeV, and tight fabrication tolerances. The latter is associated with micron-level accuracy and further waveguide frequency tuning process, both increasing its costs dramatically. By implying a novel split structure fabrication approach, it is possible to relax these tolerances to the values of 10–20 μm and eliminate the tuning step, greatly reducing their total costs. Finally, this paper presents the results of microwave measurements of split X- and Ku-band accelerating structures of different types and discusses the benefits of our fabrication approach.

43 PARTICLE ACCELERATORS↗

Sub-MeV ultra-compact linac for radioactive isotope sources replacement, non-destructive testing, security and medical applications

RadiaBeam Technologies, LLC has developed an inexpensive, hand-portable 180 keV electron accelerator to replace 57 Co radionuclide sources in Cascade Header Enrichment Monitor detectors. We used two innovative technologies in our design: a Ku-band (1 cm wavelength) magnetron, and a split accelerating structure design to reduce manufacturing costs. In this paper, we will discuss the accelerator, including X-ray convertor and accelerating structure design. The results of RF measurements of a Ku-band split structure prototype will also be reviewed. Other applications of Ku-band linacs include compact backscatter and transmission X-ray security inspection systems, as well as computed tomography (CT) systems for luggage and parcel screening. The main requirement for luggage inspection systems is that the X-ray source must be extremely compact. Further, the required energies should cover the range from 180 keV to 1 MeV. In this paper, we will discuss the linac’s energy scalability and other modifications that will enable our technology to address these applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗