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At least 253 records · Page 14

Plasma sprayed ceramic thermal barrier coating for NiAl-based intermetallic alloys

A thermal barrier coating system consists of two layers of a zirconia-yttria ceramic. The first layer is applied by low pressure plasma spraying. The second layer is applied by conventional atmospheric pressure plasma spraying. This facilitates the attachment of a durable thermally insulating ceramic coating directly to the surface of a highly oxidation resistant NiAl-based intermetallic alloy after the alloy has been preoxidized to promote the formation of a desirable Al2O3 scale.

Miller, Robert A.↗

Laser-interference pulse number dependence of surface chemistry and sub-surface microstructure of AA2024-T3 alloy

The laser-based treatment of a metal surface is an intrinsically non-chemical technique that can alter both the topology and chemistry of surfaces. A laser-based treatment for coating and joining applications can offer alternative surface preparations to the chemically-based surface preparation techniques, which are subject to severe environmental protection and hazardous-waste management considerations. In this study, the surface chemistry and sub-surface microstructural changes are investigated for a novel surface processing method using laser interferometry produced by two beams of a pulsed Nd:YAG laser. The two-beam laser-interference allowed the structuring of the surface at length scales much less than that of the laser beam spot. Surface chemistry changes in the oxide layer of AA 2024-T3 aluminum alloy rolled sheet due to laser processing were investigated using x-ray photoelectron spectroscopy (XPS). Near surface microstructural changes have been investigated with scanning electron microscopy and energy dispersive x-ray spectroscopy (SEM/EDS), and scanning transmission electron microscopy (STEM) as a function of number of interfering laser shots. SEM microstructure pictures of the top surface shows the minimization of surface defects, as all of the sharp features from a rolled sheet surface were smoothed by laser-structuring. STEM images indicate that the laser-interference processing reduced the formation of CuMn-rich precipitates over a 500–800 nm depth from the top surface. XPS data indicated that the Al oxide layer is modified compared to that of the baseline specimen and that the oxide thickness increases with the number of shots per spot. Finally, the additional thicker oxide on Al alloys is expected to increase the corrosion resistance of the coated Al 2024.

36 MATERIALS SCIENCE↗

Temperature-Dependent Sn Incorporation and Defect Formation in Pseudomorphic SiSn Layers on Si (001) via Molecular Beam Epitaxy

SiSn alloys have attracted growing interest for group-IV bandgap engineering, although their epitaxial growth remains challenging due to the extremely low equilibrium solubility of Sn in Si. In this work, fully strained (pseudomorphic) SiSn epitaxial layers were grown on Si (001) substrates by means of molecular beam epitaxy. A systematic investigation reveals a strong inverse correlation between growth temperature and Sn incorporation efficiency. Despite a constant Sn flux, the incorporated Sn composition decreases from 5.5% to 3.2% as the growth temperature increases, indicating a pronounced temperature dependence of Sn incorporation. Reflection high-energy electron diffraction indicates a gradual transition of the growth from two-dimensional to three-dimensional with increasing film thickness. Structural characterization by means of X-ray diffraction, atomic force microscopy, and transmission electron microscopy confirms the pseudomorphic growth and smooth surface morphology and reveals twins and stacking faults near the surface region. These results establish a quantitative reference for SiSn growth kinetics and provide guidance for future studies of SiSn and SiGeSn alloys in silicon-compatible electronic and optoelectronic applications.

SiSn alloys↗

Bond Synergy Model for Bond Energies in Alloy Oxides

In this work we introduce a metal-oxide bond-energy model for alloy oxides based on pure-phase bond energies and bond synergy factors that describe the effect of alloying on the bond energy between cations and oxygen, an important quantity to understand the formation of alloy oxides and their composition. This model is parameterized for binary cation-alloy oxides using density-functional theory energies and is shown to be directly transferable to multi-component alloy oxides. We parameterized the model for alloy oxide energies with metal cations that form the basis of corrosion resistant alloys, including Fe, Ni, Cr, Mo, Mn, W, Co, and Ru. We find that isoelectronic solutes allow quantification of pure-phase bond energies in oxides and the calculated bond energy values give sensible results compared to common experience, including the role of Cr as the passive-layer former in Fe–Ni–Cr alloys for corrosion applications. Additionally, the bond synergy factors give insights into the mutual strengthening and weakening effects of alloying on cation-oxygen bonds and can be related to enthalpy of mixing and charge neutrality constraints. We demonstrate how charge neutrality can be identified and achieved by the oxidation states that the different cations assume depending on alloy composition and the presence of defects.

Electrochemistry↗

Oxygen Reduction at PtNi Alloys in Direct Methanol Fuel Cells—Electrode Development and Characterization

Catalyst layers made from novel catalysts must be fabricated in a way that the catalyst can function to its full potential. To characterize a PtNi alloy catalyst for use in the cathode of Direct Methanol Fuel Cells (DMFCs), the effects of the manufacturing technique, ink composition, layer composition, and catalyst loading were here studied in order to reach the maximum performance potential of the catalyst. For a more detailed understanding, beyond the DMFCs performance measurements, we look at the electrochemically active surface area of the catalyst and charge-transfer resistance, as well as the layer quality and ink properties, and relate them to the aspects stated above. As a result, we make catalyst layers with optimized parameters by ultrasonic spray coating that shows the high performance of the catalyst even when containing less Pt than commercial products. Using this approach, we can adjust the catalyst layers to the requirements of DMFCs, hydrogen fuel cells, or polymer electrolyte membrane electrolysis cells.

30 DIRECT ENERGY CONVERSION↗

Lattice-Mismatched van der Waals Epitaxy and Photoluminescence of Two-Dimensional GaxIn1-xSe Alloys on Si(111)

GaxIn1-xSe (GIS) alloys are two-dimensional (2D) layered materials with band gaps and lattice parameters of interest for many energy and electronic applications. They can be fabricated using van der Waals epitaxy, which is an emerging technique that offers unprecedented opportunities for 2D optoelectronic devices and epitaxy processes. This work has demonstrated van der Waals epitaxy of GIS alloys for the first time. Films with x compositions of 0, 0.062, 0.164, 0.680, 0.894, and 1 and tunable lattice constants were grown on Si(111) substrates, and characterized by X-ray diffraction pole figure and transmission electron microscope analysis. In spite of the lattice mismatches (InSe is 4.1% too large and GaSe is 2.8% too small), these alloys grow epitaxially, with Si(111) || GIS(001) and Si[1-10] || GIS[100] orientation. Photoluminescence was used to measure tunable band gaps in the absorber-relevant 1.3-2.0 eV range as a function of x composition and showed GIS did not degrade after capping with Se and prolonged storage. Therefore, GIS alloys exhibit a technologically advantageous combination of tunable band gap and photoluminescence with relaxed lattice parameter and rotational registry with the substrate.

36 MATERIALS SCIENCE↗

Low Energy Implantation into Transition-Metal Dichalcogenide Monolayers to Form Janus Structures

Atomically-thin two-dimensional (2D) materials face significant energy barriers for synthesis and processing into functional metastable phases such as Janus structures. Here, in this study, the controllable implantation of hyperthermal species from pulsed laser deposition (PLD) plasmas is introduced as a top-down method to compositionally engineer 2D monolayers. The kinetic energies of Se clusters impinging on suspended monolayer WS 2 crystals were controlled in the <10 eV/atom range with in situ plasma diagnostics to determine the thresholds for selective top layer replacement of sulfur by selenium for the formation of high quality WSSe Janus monolayers at low (300 °C) temperatures, and bottom layer replacement for complete conversion to WSe 2 . Atomic-resolution electron microscopy and spectroscopy in tilted geometry confirm the WSSe Janus monolayer. Molecular dynamics simulations reveal that Se clusters implant to form disordered metastable alloy regions, which then recrystallize to form highly ordered structures, opening the door for low-energy implantation by PLD as a novel method to explore the synthesis of 2D Janus layers and alloys of variable composition.

2D materials↗

Joining lead wires to thin platinum alloy films

A two step process of joining a lead wire to .000002 m thick platinum alloy film which rests upon an equally thin alumina insulating layer which is adhered to a metal substrate is described. Typically the platinum alloy film forms part of a thermocouple for measuring the surface temperature of a gas turbine airfoil. In the first step the lead wire is deformed 30 to 60% at room temperature while the characteristic one million ohm resistance of the alumina insulating layer is monitored for degradation. In the second step the cold pressed assembly is heated at 865 to 1025 C for 4 to 75 hr in air. During the heating step any degradation of insulating layer resistance may be reversed, provided the resistance was not decreased below 100 ohm in the cold pressing.

Przybyszewski, J. S.↗

Influence of copper and aluminum substitution on high-temperature oxidation of the FeCoCrNiMn “Cantor” alloy

In this study, the oxidation behavior of FeCoCrNiMn (HEA + Mn) is compared to three modified HEAs manufactured by substituting Mn with Al, Cu, or Al + Cu. Oxidation tests were conducted between 600°C and 800°C for up to 500 h in synthetic air. Substitution of Mn leads to a significant improvement in the oxidation resistance for the three modified HEAs. For FeCoCrNiCu (HEA + Cu), a local attack of a Cu-rich phase was observed, leading to the formation of CuO blisters on the surface. The FeCoCrNiAl (HEA + Al) alloy was characterized by the formation of a thin Al 2 O 3 surface layer for all temperatures. However, for the HEA + Al alloy the formation of AlN was observed after 300 h at 800°C, leading to a partial breakdown of the protective scale. FeCoCrNiCuAl (HEA + Cu + Al) by far showed the best oxidation resistance, characterized by the formation of a highly protective Al 2 O 3 scale that effectively inhibited nitrogen penetration into the metal subsurface and local attack of the Cu-rich phase.

36 MATERIALS SCIENCE↗

Metallurgical Mechanisms Controlling Mechanical Properties of Aluminum Alloy 2219 Produced by Electron Beam Freeform Fabrication

The electron beam freeform fabrication (EBF3) layer-additive manufacturing process has been developed to directly fabricate complex geometry components. EBF3 introduces metal wire into a molten pool created on the surface of a substrate by a focused electron beam. Part geometry is achieved by translating the substrate with respect to the beam to build the part one layer at a time. Tensile properties demonstrated for electron beam deposited aluminum and titanium alloys are comparable to wrought products, although the microstructures of the deposits exhibit cast features. Understanding the metallurgical mechanisms controlling mechanical properties is essential to maximizing application of the EBF3 process. Tensile mechanical properties and microstructures were examined for aluminum alloy 2219 fabricated over a range of EBF3 process variables. Unique microstructures were observed within the deposited layers and at interlayer boundaries, which varied within the deposit height due to microstructural evolution associated with the complex thermal history experienced during subsequent layer deposition. Microstructures exhibited irregularly shaped grains with interior dendritic structures, described based on overall grain size, morphology, distribution, and dendrite spacing, and were correlated with deposition parameters. Fracture features were compared with microstructural elements to define fracture paths and aid in definition of basic processing-microstructure-property correlations.

Domack, Marcia S.↗

Environmental Protection Coating System for Refractory Metal Alloys (EPCS for RMAs)

As part of ARPA-E’s Ultra High Temperature Impervious Materials Advancing Turbine Efficiency (UITIMATE) program, this project aims to develop an environmental protection coating system (EPCS) for refractory metal alloys (RMAs) – which will provide radical improvement in long term protection for ultra-high temperature refractory metal components in harsh gas-turbine environments. The drive for higher fuel efficiency and higher core power of gas turbines used in electric power generation and in aircraft propulsion requires higher peak operation temperatures. The temperature capability of state-of-the-art materials cannot meet the new requirements. Refractory metal alloys have desirable capabilities for achieving the required peak temperatures, but most of them are subject to oxidation in the gas turbine environment. Thus, there is a strong need to develop novel environmental protective coatings that enable the refractory metals to operate in an ultra-high temperature engine environment. This project is composed of four major technical innovations that can provide a potentially transformational solution in providing environmental protection for refractory metal alloys over a wide range of temperature. 1) Multi-layer self-healing environmental barrier coating (EBC) that provides protection against combustion gas environment. 2) Oxidation resistant diffusion barrier (DB) on the alloy surface to enhance coating stability. 3) Synergistic integration of the multi-layer self-healing EBC with the diffusion barrier to extend coating life. 4) Guidance of physics-based modeling to accelerate coating development and optimization. Our team has successfully developed a multi-layer self-healing environmental protection coating system (EPCS) that can provide oxidation protection for commercially available molybdenum based refractory metal alloys over a wide temperature range of up to 1600 °C for fuel-efficient gas turbine applications. The team also developed a multi-layer high temperature coating design tool to accelerate coating development and optimization based on physics-based modeling. The team also engaged RTX business unite, notable Pratt and Whitney, for future commercialization of this technology. The successful completion of this Phase I effort led to the selection of performing Phase II of the program. In Phase II, the team plans to apply the EPCS in the protection of a newly discovered molybdenum-based metal alloy which has the potential of superior high temperature properties to the commercial products. Th coating will be evaluated under test conditions and environment that mimic gas turbine operation.

36 MATERIALS SCIENCE↗

Enhancing corrosion resistance of lightweight metal alloys through laser shock peening

In this study, we investigated the effects of laser shock peening (LSP) on the corrosion resistance of lightweight metal alloys, specifically AA6061 and AZ31. LSP was performed underwater, using a nanosecond pulse laser and without using a protective coating or layer on the workpiece. The corrosion behaviors of these alloys were analyzed through electrochemical tests, including open circuit potential, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements. The results demonstrated that LSP significantly improved the polarization resistance, and higher laser power intensities led to increased corrosion resistance and reduced corrosion rates. This enhancement in anti-corrosion performance is attributed to the formation of a protective oxide layer on the surface, acting as a barrier against corrosion. In conclusion, the findings underscore the potential of laser surface treatment as a viable technique for enhancing the corrosion resistance of lightweight metal alloys.

36 MATERIALS SCIENCE↗

Characterization of Brazed Joints of C-C Composite to Cu-clad-Molybdenum

Carbon-carbon composites with either pitch+CVI matrix or resin-derived matrix were joined to copper-clad molybdenum using two active braze alloys, Cusil-ABA (1.75% Ti) and Ticusil (4.5% Ti). The brazed joints revealed good interfacial bonding, preferential precipitation of Ti at the composite/braze interface, and a tendency toward de-lamination in resin-derived C-C composite due to its low inter-laminar shear strength. Extensive braze penetration of the inter-fiber channels in the pitch+CVI C-C composites was observed. The relatively low brazing temperatures (<950 C) precluded melting of the clad layer and restricted the redistribution of alloying elements but led to metallurgically sound composite joints. The Knoop microhardness (HK) distribution across the joint interfaces revealed sharp gradients at the Cu-clad-Mo/braze interface and higher hardness in Ticusil (approx.85-250 HK) than in Cusil-ABA (approx.50-150 HK). These C-C/Cu-clad-Mo joints with relatively low thermal resistance may be promising for thermal management applications.

Singh, M.↗

Corrosion analysis of Al-Ce-Ni and Al-Cu-Ce cast alloys in dilute boric acid at room and elevated temperatures

Two Al-Ce-Ni cast alloys, and an Al-Cu-Ce cast alloy, as candidate wet storage materials for spent nuclear fuels, were tested in 0.23 wt% H 3 BO 3 solution to assess the alloy corrosion resistance. Electrochemical and gravimetric corrosion data suggest that the three Al alloys are unlikely to undergo any severe corrosion in dilute H 3 BO 3 at or below 50 °C. Post-exposure characterization of the three Al alloys, including scanning and transmission electron microscopy and electron dispersive spectroscopy, revealed a corrosion product layer, mostly Al 2 O 3 , on the exposed surface and local penetration of oxygen into the alloy matrix. The degree of oxide layer growth and oxygen penetration is greater at 80 °C than the temperature at/below 50 °C. The Al-Cu-Ce alloy is considered less corrosion resistant than the other two alloys studied.

Al-Ce alloy↗

Milestone 1.2.14: Surface Characterization of Irradiated Surrogate Non-Native Corrosion Plumes on Aluminum 6061-T6 Specimens

The United States Department of Energy is seeking to evaluate the feasibility of extended dry storage of aluminum-clad spent nuclear fuel (ASNF) in helium-backfilled cannisters. A significant research effort has been devoted to determining the amount of radiation-induced molecular hydrogen generation from corrosion layers that would be present on the fuel assembly surfaces. However, to date, no evidence of radiation-induced changes in the microstructure of the corroded aluminum surfaces have been reported. This report provides surface characterization, in terms of corrosion layer composition and morphology, for aluminum alloy 6061-T6 “plume” samples subjected to one of three potential ASNF drying techniques—“vacuum only”, “vacuum + 4 hours at 100 oC”, and “vacuum + 4 hours at 220 oC”—and gamma irradiated (= 53 MGy) in the presence of helium gas with ~0% added relative humidity. At these high absorbed gamma doses, for the first time ever, radiation-induced circular defects were found on the sample surface, regardless of the drying regime employed. Additionally, large cracks that penetrated through the corrosion layer to expose bare aluminum metal were observed in irradiated “plume” specimens subjected to drying conditions of “vacuum + 4 hours at 220 oC”. The nature and implications of these defects on the extended dry storage of ASNF is unclear, requiring further study.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

How surface damage removal affects fatigue life

The effect of the removal of work hardened surface layers from specimens of 2024-T4 aluminum alloy and AISI-4130 steel on their fatigue lives has been investigated. Specimens were fatigued at selected stress levels for a given number of cycles, and the surface layer was removed followed by subsequent fatigue cycling. Results confirm that when a material is subjected to fatigue loading, damage accumulates in the surface layers in the form of work hardening. Removal of the surface layer brings the specimen back to its pre-fatigued condition.

Jeelani, S.↗

Effect of mechanical surface and heat treatments on erosion resistance

The effect of erosion by glass beads and crushed glass and by heat treatments on the erosional resistance of 6061 aluminum alloy and 1045 steel were studied. The aluminum alloy's erosion resistance was found to be insensitive to mechanical surface treatment applied before testing, and was determined to depend on the properties of the work-hardened surface layer; this was also demonstrated for aluminum alloy single crystals. The aluminum alloy heat treatments included annealing, solution, and precipitation. Solution was found to increase erosion resistance but precipitation had the opposite effect. Hardness showed no correlation with erosion resistance for either aluminum alloy steel. The steel tests showed that crushed glass provides an order of magnitude more erosion than glass beads.

Salik, J.↗

Direct Synthesis of Layer-Tunable and Transfer-Free Graphene on Device-Compatible Substrates Using Ion Implantation Toward Versatile Applications

Direct synthesis of layer-tunable and transfer-free graphene on technologically important substrates is highly valued for various electronics and device applications. State of the art in the field is currently a two-step process: a high-quality graphene layer synthesis on metal substrate through chemical vapor deposition (CVD) followed by delicate layer transfer onto device-relevant substrates. Here, we report a novel synthesis approach combining ion implantation for a precise graphene layer control and dual-metal smart Janus substrate for a diffusion-limiting graphene formation to directly synthesize large area, high quality, and layer-tunable graphene films on arbitrary substrates without the post-synthesis layer transfer process. Carbon (C) ion implantation was performed on Cu–Ni film deposited on a variety of device-relevant substrates. A well-controlled number of layers of graphene, primarily monolayer and bilayer, is precisely controlled by the equivalent fluence of the implanted C-atoms (1 monolayer ~4 × 10 15 C-atoms/cm 2 ). Upon thermal annealing to promote Cu-Ni alloying, the pre-implanted C-atoms in the Ni layer are pushed toward the Ni/substrate interface by the top Cu layer due to the poor C-solubility in Cu. As a result, the expelled C-atoms precipitate into a graphene structure at the interface facilitated by the Cu-like alloy catalysis. After removing the alloyed Cu-like surface layer, the layer-tunable graphene on the desired substrate is directly realized. The layer-selectivity, high quality, and uniformity of the graphene films are not only confirmed with detailed characterizations using a suite of surface analysis techniques but more importantly are successfully demonstrated by the excellent properties and performance of several devices directly fabricated from these graphene films. Molecular dynamics (MD) simulations using the reactive force field (ReaxFF) were performed to elucidate the graphene formation mechanisms in this novel synthesis approach. With the wide use of ion implantation technology in the microelectronics industry, this novel graphene synthesis approach with precise layer-tunability and transfer-free processing has the promise to advance efficient graphene-device manufacturing and expedite their versatile applications in many fields.

36 MATERIALS SCIENCE↗