Al Oxide Layer Research Articles

Dynamic behaviors of interfacial oxides and elements during the ultrasonic-assisted diffusion bonding of 6063Al alloys

Efficiently breaking the oxide layer and rapidly diffusing of elements at low-temperature has been a longstanding goal in the diffusion bonding (DB) of Al alloys. To break the interfacial oxide layers and accelerate atomic diffusion, ultrasound energy was introduced during the DB of 6063Al. A full Zn–Al eutectoid joint was manufactured via a pure Zn interlayer at 360 °C in atmospheric by an ultrasonic-assisted diffusion bonding (U-DB) at only an ultrasonic vibration of10 min. During U-DB, brittle cracks were formed in the interfacial oxide layers due to high strain rate induced by ultrasonic action. Zn diffused into Al alloy through the brittle cracks in oxide layers via “subcutaneous diffusion,” forming a Zn–Al eutectoid diffusion region between the Al alloy and oxide layer. The oxide fragments irregularly migrated to the center of the joint due to Kirkendall effect and ultrasonic action, finally dispersed in the bonded metal. The bonded metal finally transformed as a full Zn–Al eutectoid phase after consuming interlayer. The shear strength of the Zn–Al eutectoid joint reached 82.6 MPa. The Zn–Al mutual diffusion coefficient of U-DB at 360 °C was ∼0.6 μm2/s, which was about 20 times higher than the thermal diffusion coefficient under same temperature condition. Additionally, the mechanism of ultrasonic-assisted diffusion based on the strain-driven diffusion mode was discussed in detail.

Photoemission Study on Si and Ge Segregation on Al/Si0.8Ge0.2 Structures

We have demonstrated the formation of an ultrathin Si and Ge layer on an Al/Si0.8Ge0.2(111) structure caused by controlling the annealing condition. From the XPS characteristics, the annealing temperature, rather than the time, was found to be important in controlling the Si and Ge segregation. Also, by thermal annealing in N2 ambient, the segregated Ge on the Al/Si0.8Ge0.2 structure was found to be stable and resistant to oxidation due to the surface Al oxide layer and the segregated Si. We also found that Ge atoms were highly selectively segregated from the Al/Si0.8Ge0.2(111) structure below 500ºC. It was also found that Ge atoms could be selectively segregated from the Al/Si0.8Ge0.2(111) structure by rapid thermal annealing. The results will lead to the development of two-dimensional Ge crystals that are highly compatible with Si ultra-large-scale integration processing.

Sustainable super-hard and thick nanodiamond composite film deposited on cemented carbide substrates with an interfacial Al-interlayer

Super-hard nanodiamond composite (NDC) films, synthesized via cathodic arc plasma deposition on unheated WC − Co substrates, offer an eco-friendly solution for cutting tools. A 100 nm-thick Al-interlayer mitigates Co catalytic effects, improving adhesion and yielding smooth and dense 10 µm-thick films at a deposition rate of 3.3 μm/hr. These grain-boundary-rich nanostructured films, with an impressive 58 GPa hardness attributed to a substantial 70 % C sp3 fraction, prove optimal for hard coatings. The Al-interlayer effectively suppresses Co catalytic effects, forming a dense Al-oxide layer, enhancing film hardness and adhesion (Lcr = 18.6 N). NDC films present a promising eco-friendly option for high-performance hard coatings.

Investigation on indirect laser welding of copper to aluminum

Laser beam welding of aluminum (Al) to copper (Cu) is challenging due to the formation of intermetallic compounds that are brittle and have high resistivities. However, the Cu/Al phase diagram shows a region were solubility of Cu in Al is present and, on the other hand, a region with the formation of a eutectic phase between α-Al and Al2Cu is present as well. Targeting this area turned to be advantageous for solid state welding, as shown for probeless Friction-Stir-Spot-Welding realizing ductile joints between Al and Cu.In this paper an approach based on indirect laser welding of Cu with Al will be presented and discussed. A green laser was used in order to join Cu to Al in lap joint configuration. The laser beam irradiates the Cu surface, whereby the formation of a common melt pool between Cu and Al is avoided. The heat input and the temperature gradient are assumed to support diffusion at the interface between Cu and Al forming a near eutectic layer. Indeed, a melting layer is formed at the interface between Cu and Al supporting joint formation based on a firmly bonding between both materials. The solidified layer presents a copper rich area towards the copper sheet with plate-like structures of Al2Cu, a region with α-Al crystals on the aluminum side and a eutectic layer of lamellar Al2Cu and α-Al in between. The described morphology is very similar to investigations on probeless Friction-Stir-Spot-Welding, whereas a very low pressure is adopted in indirect laser welding and Al-oxide layer seems not to act as a barrier for joint formation.

Enhancing NaBH4 regeneration using an Al-rich alloy

Onsite hydrogen generation by sodium borohydride hydrolysis resolves hydrogen energy supply system challenges. However, the spent-NaBH4 regeneration is still a problem in the closed loop of this irreversible reaction. As the by-product is the key to the problem, NaB(OH)4 is regarded as not the boron source but the hydrogen source of NaBH4 regeneration. Therefore, in this study, inexpensive Al metal and NaB(OH)4 are ball milled under argon to regenerate NaBH4 without additional hydrogen input. However, the ball-milling reaction is hindered by the flexible Al and impact oxide layer, and the NaBH4 yield is only approximately 22 %. Therefore, a brittle intermetallic compound Mg2Al3 is reacted with NaB(OH)4 by ball milling, achieving a NaBH4 yield of over 42 %. The mechanism study shows that the brittleness of the raw material plays an important role in promoting the ball-milling reaction. This study achieves NaBH4 regeneration using only Al as the reducing agent and provides a promising method to promote the mechanochemical regeneration of NaBH4.

Effect of grain refinement on high temperature steam oxidation of an FeCrAl alloy

FeCrAl alloys are promising candidates to replace Zr alloys as fuel cladding materials in nuclear light-water reactors. Grain refinement has been indicated to improve irradiation resistance. To enhance corrosion resistance as well, the effects of grain refinement on steam corrosion behavior were investigated in this work. Samples of Kanthal D alloy (Fe-21Cr-5Al) with two different grain sizes (coarse-grained and ultrafine-grained) were exposed to steam at 1200 °C for 2 hrs. Results indicate improved steam corrosion resistance in ultrafine-grained Kanthal D with formation of a thinner protective Al oxide layer and the presence of a thin underlying Cr oxide layer.

Proof of Concept: The GREENcell—A Lithium Cell with a F-, Ni- and Co-Free Cathode and Stabilized In-Situ LiAl Alloy Anode

Given the rising upscaling trend in lithium-ion battery (LiB) production, there is a growing emphasis on the environmental and economic impacts alongside the high energy density demands. The cost and environmental impact of battery production primarily arise from the critical elements Ni, Co, and F. This drives the exploration of Ni-free and Co-free cathode alternatives such as LiMn2O4 (LMO) and LiFePO4 (LFP). However, the absence of Ni and Co results in reduced capacity and insufficient cyclic stability, particularly in the case of LMO due to Mn dissolution. To compensate for both low cathode capacitance and low cycle stability, we propose the GREENcell, a lithium cell combining a F-free polyisobutene (PIB) binder-based LMO cathode with a stabilized in -situ LiAL alloy anode. A LiAl alloy anode with the chemical composition of LiAl already shows a theoretical capacity of 993 Ah·kg−1. Therefore, it promises extraordinarily higher energy densities compared to a commercial graphite anode with a capacity of 372 Ah·kg−1. Following an iterative development process, different optimization strategies, especially those targeting the stability of the Al-based anode, were evaluated. During Al foil selection, foil purity and thickness could be identified as two of the dominant influencing parameters. A pressed-in stainless steel mesh provides both mechanical stability to the anode and facilitates alloy formation by breaking up the Al oxide layer beforehand. Additionally, a binder-stabilized Al oxide or silicate layer is pre-coated on the Al surface, posing as a SEI-precursor and ensuring a uniform liquid electrolyte distribution at the phase boundary. Employing a commercially available Si-containing Al alloy mitigated the mechanical degradation of the anode, yielding a favorable impact on long-term stability. The applicability of the novel optimized GREENcell is demonstrated using laboratory coin cells with LMO and LFP as the cathode. As a result, the functionality of the GREENcell was demonstrated for the first time, and thanks to the anode stabilization strategies, a capacity retention of >70% after 200 was achieved, representing an increase of 32.6% compared to the initial Al foil.

Ammonia decomposition over Ru-coated metal-structured catalysts for COx-free hydrogen production

We report the development of Ru/Mg–Al oxide coated metal-structured catalysts with excellent heat and mass transfer characteristics for efficient clean H2 production from ammonia decomposition. Ammonia is a promising carrier for the mass transport of hydrogen and facilitates the production of COx-free hydrogen by decomposing into nitrogen and hydrogen. Ru nanoparticles are uniformly dispersed on the Mg–Al oxide layer of the FeCralloy monoliths and foams via precipitation. The catalytic activities depend on the surface area and loading of the catalysts and the metal dispersion in the oxide layer. At temperatures <650 °C, and a gas hourly space velocity (GHSV) of 3,000 h−1, monolithic catalysts with a large surface area and evenly distributed active metals perform excellently. Foam catalysts with excellent heat transfer performance better at temperatures >650 °C and GHSV >6,000 h−1. Foam catalyst stability is verified for 100 h in a 20 Nm3/h high-purity hydrogen production system.

Simulations on the oxidation of Al-Mg alloy nanoparticles using the ReaxFF reactive force field

Nanoalloy holds multiple complex morphologies in combustion. However, the underlying mechanism, which is crucial to advance technical application of the nanoalloy, remains a challenging mystery. Herein, we performed a ReaxFF reactive molecular dynamics simulation on Al-Mg alloy nanoparticles (AMNPs) as a case study to further analyze oxidation behavior. Results showed that the evolution of AMNPs in combustion can be divided into three stages: (1) AMNPs first undergo phase separation and aggregate into Mg and Al phases; (2) Mg atoms rapidly diffuse to the surface and are oxidized; (3) Oxygen atoms diffuse inward and oxidize Al atoms. The inward diffusion of oxygen atoms is particularly hindered at the interface between Mg oxide shell and Al oxide layer. AMNPs prefer to form internal hollow structures at lower temperature and high oxygen concentration. The outward diffusion of Mg atoms causes the core to be gradually hollowed out. The spilled Mg atoms are oxidized and attached to the surface of alumina. The structure of Mg oxide (surface layer)-Al oxide (middle layer)-hollow (core) is finally formed. In addition, micro-explosion and external Mg oxide shell inhibit the agglomeration of nanoparticles. The study provides insight into the complex interactions between Al-Mg nanoalloy and oxygen.

The Effect of Aluminum Oxide Layer and Annealing Atmosphere on Diffusion Behavior of Ni/Al Film

Power devices, such as power conversion and control devices, with excellent performance and high efficiency, are essential to realizing a carbon-neutral society. Towards that goal, devices using wide bandgap semiconductors, such as SiC and GaN, are being developed. Because wide bandgap semiconductors can operate at higher temperatures than conventional Si devices can, packaging technology with high heat resistance is required to demonstrate their performance. Previously, we proposed a sinter bonding technique using Ni nanoparticles for die bonding, i.e., bonding semiconductor chips to substrates. We demonstrate that Ni could be bonded to Al by sintering in the air. Meanwhile, the structures of recently reported power devices contain surface electrodes with an Al-Ni interface. Our research on Ni nanoparticle bonding and the Al-Ni interface in recent device structures demonstrated that evaluating the changes in the Al-Ni interface at high temperatures is crucial to ensure long-term reliability for high-temperature operation of the devices. Therefore, the diffusion behavior of Ni/Al multilayer samples annealed in air or vacuum was evaluated using Auger electron spectroscopy. Furthermore, the effect of the natural Al oxide film at the Ni/Al interface was also investigated. The results revealed that in the Ni/Al2O3/Al structure, atmospheric heating induced interdiffusion of Ni and Al through the Al oxide layer and that the natural Al oxide layer acted as a barrier to diffusion during vacuum heating.

Formation mechanisms of surface blistering in AA6xxx rolled products: microstructure characterisation, ultrasonic analysis, and rolling tests results

ABSTRACT The source of surface blister defect in 6xxx series Al rolled products was studied. A blister defect, aligned with the rolling direction, was observed on the surface of the AA6xxx Al rolled sheets. It was indicated that the porosities and small microstructural inhomogeneities inside the cast ingots, identified by ultrasonic tests and metallography analysis, were not the origin of these surface defects. Pilot scale rolling trials indicated that the blister defects were correlated with the longitudinal internal casting cracks. The short side cracks in the cast ingots, covered by a thin Al oxide layer, were not healed and remained partially open after the rolling process. The unhealed cracks served as the nucleation sites for H2 precipitation during the later stages of the thermomechanical process, which were subsequently resulted from surface blisters on the AA6xxx Al rolled sheets.

Concurrent changes in constituent and B type-like crack of PEO-treated Al-oxide layer by static post-annealing

The concurrent changes of both constituent and critical defect in the Al-oxide layer formed by plasma electrolytic oxidation (PEO) down to 268 K, at which the occurrence of discharge channel would be inhibited effectively, were investigated with respect to post-treatment at annealing temperatures ranging from 473 to 673 K. With an increase in annealing temperature, the appreciable defect-channels of relatively dense PEO-treated layer was detected at 673 K since the dehydration reaction from α- and γ-Al(OH)3 to γ-Al2O3 gave rise to the change in lattice volume. Such defect was defined as B type-like channel that would accelerate the corrosion failure by harmful Cl− ions. In contrast, the corrosion potential of PEO-treated layer increased by lowering the Al(OH)3/γ-Al2O3 ratio due to thermal transformation. Hence, the excellent corrosion resistance was attained on the PEO-treated sample annealed at 573 K where the concurrent evolutions of constituent compounds and B type-like crack were in balance.

The growth and nanothermite reaction of 2Al/3NiO multilayer thin films

Nanothermite NiO–Al is a promising material system for low gas emission heat sources; yet, its reactive properties are highly dependent on material processing conditions. In the current study, sputter deposition is used to fabricate highly controlled nanolaminates comprised of alternating NiO and Al layers. Films having an overall stoichiometry of 2Al to 3NiO were produced with different bilayer thicknesses to investigate how ignition and self-sustained, high temperature reactions vary with changes to nanometer-scale periodicity and preheat conditions. Ignition studies were carried out with both hot plate and laser irradiation and compared to slow heating studies in hot-stage x-ray diffraction. Ignition behavior has bilayer thickness and heating rate dependencies. The 2Al/3NiO with λ ≤ 300 nm ignited via solid/solid diffusion mixing (activation energy, Ea = 49 ± 3 kJ/mole). Multilayers having λ ≥ 500 nm required a more favorable mixing kinetics of solid/liquid dissolution into molten Al (Ea = 30 ± 4 kJ/mole). This solid/liquid dissolution Ea is a factor of 5 lower than that of the previously reported powder compacts due to the elimination of a passivating Al oxide layer present on the powder. The reactant mixing mechanism between 300 and 500 nm bilayer thicknesses was dependent on the ignition source's heating rate. The self-propagating reaction velocities of 2Al/3NiO multilayers varied from 0.4 to 2.5 m/s. Pre-heating nanolaminates to temperatures below the onset reaction temperatures associated with forming intermediate nickel aluminides at multilayer interfaces led to increased propagation velocities, whereas pre-heating samples above the onset temperatures inhibited subsequent attempts at laser ignition.

Anodizing Al–Si Foundry Alloys: A Critical Review

Compared with pure aluminum and wrought aluminum alloys, Al foundry alloys are more difficult to be anodized. The high content of alloying elements prevents the uniform growth of the Al oxide layer and enhances the embedding of defects in the anodic film. The microstructure of the substrate and the anodizing parameters play a key role in the final quality of the oxide layer. Variations in the chemical composition, casting process, and pre‐ and post‐anodizing treatments can significantly affect the anodizing response. This work aims to critically review the main factors influencing the growth and morphology of the anodic layer in Al–Si foundry alloys. In particular, the effects on the oxide thickness, surface mechanical properties, and corrosion resistance are discussed in detail.

Addition of Fe3O4 as electron mediator for enhanced cementation of Cd2+ and Zn2+ on aluminum powder from sulfate solutions and magnetic separation to concentrate cemented metals from cementation products

The zinc leach residues (ZLRs) generated by Zn hydrometallurgical process are disposed of in landfills due to a lack of proper treatment methods although they contain toxic heavy metals like Cd and Zn. To remove these heavy metals, this study investigated cementation using aluminum (Al) together with magnetite (Fe3O4) from sulfate solutions. Cementation using only Al could not remove Cd2+ and Zn2+ because the insulating Al oxide (Al2O3) layer on Al surface was not removed at high pH (5.0) from sulfate solution, and inhibiting electron transfer from Al to metal ions. The addition of Fe3O4, however, enhanced the cementation of Cd2+ and Zn2+ from 0% to 83% and 92%, respectively. The results of SEM-EDS analysis for the cementation products confirmed that Cd and Zn were deposited on Fe3O4 attached on Al surface. Electrochemical impedance spectra for Al electrode in sulfate solutions confirmed that charge transfer resistance decreased when Fe3O4 powder was attached on the electrode surface, suggesting that Fe3O4 acts as a mediator to enhance electron transfer from Al to metal ions in solutions. By applying magnetic separation for the cementation products, the majority of cemented Cd and Zn were recovered together with Fe3O4 in magnetic fraction, and they were separated from Al in non-magnetic fraction.

Origin of operating voltage increase in deep UV light-emitting diodes with ITO/Al reflector

In an attempt to further elucidate the operating voltage increase in a vertical UV-C LED with p-electrode composed of transparent conducting Sn-doped indium oxide (ITO)/Al reflector, the interface formation between ITO and Al thin film was studied by using scanning transmission electron microscopy in combination with electron energy loss spectroscopy. It was confirmed that the oxidized layer was formed at the interface of the ITO/Al electrode in accordance with the thermal annealing. It was found that not only the thickness of oxide formation grew with the increased annealing temperature, the content of oxygen also increased. Moreover, it was also ascertained that the prolonged annealing time at high temperature induced the indium diffusion into the Al-oxide layer.

Electrografting of 4-Nitrobenzenediazonium Salts on Al-7075 Alloy Surfaces-The Role of Intermetallic Particles.

In this work, the electrografting of Al-7075 aluminium alloy substrates with 4-nitrobenzenediazonium salt (4-NBD) films was studied on a complex aluminium alloy surface. Prior to the electrografting reaction, the substrates were submitted to different surface treatments to modify the native aluminium oxide layer and unveil intermetallic particles (IMPs). The formation of the 4-NBD films could be correlated with the passive film state and the distribution of IMPs. The corresponding electrografting reaction was performed by cyclic voltammetry which allowed the simultaneous analysis of the redox reaction by a number of complementary surface-analytical techniques. Spatially resolved thin film analysis was performed by means of SEM-EDX, AFM, PM-IRRAS, Raman spectroscopy, XPS, and SKPFM. The collected data show that the 4-NBD film is preferentially formed either on the Al oxide layer or the IMP surface depending on the applied potential range. Potentials between −0.1 and −1.0 VAg/AgCl mostly generated nitrophenylene films on the oxide covered aluminium, while grafting between −0.1 and −0.4 VAg/AgCl favours the growth of these films on IMPs.

Phase Composition of Al-Si Coating from the Initial State to the Hot-Stamped Condition.

The chemical and phase composition of the coating and the coating/substrate interface of an Al-Si-coated 22MnB5 hot stamped steel was investigated by means of SEM-EDS, XRD, micro-XRD and electron diffraction. Moreover, the surface profile was analyzed by XPS and roughness measurements. The XPS measurements showed that the thickness of the Si and Al oxide layers increased from 14 to 76 nm after die-quenching, and that the surface roughness increased as well as a result of volume changes caused by phase transformations. In addition to the FeAl(Si) and Fe2Al5 phases and the interdiffusion layer forming complex structures in the coating, electron diffraction confirmed the presence of an Fe2Al5 phase, and also revealed very thin layers of Fe3(Al,Si)C, Fe2(Al,Si)5 and Al-bearing rod-shaped particles in the immediate vicinity of the steel interface. Moreover, the scattered nonuniform layer of the Fe2Al8Si phase was identified in the outermost layer of the coating. Despite numerous studies devoted to researching the phase composition of the Al-Si coating applied to hot stamped steel, electron diffraction revealed very thin layers and particles on the coating/substrate interface and outermost layer, which have not been analyzed in detail.

Enhanced Cementation of Co2+ and Ni2+ from Sulfate and Chloride Solutions Using Aluminum as an Electron Donor and Conductive Particles as an Electron Pathway

Cobalt and nickel have become important strategic resources because they are widely used for renewable energy technologies and rechargeable battery production. Cementation, an electrochemical deposition of noble metal ions using a less noble metal as an electron donor, is an important option to recover Co and Ni from dilute aqueous solutions of these metal ions. In this study, cementation experiments for recovering Co2+ and Ni2+ from sulfate and chloride solutions (pH = 4) were conducted at 298 K using Al powder as electron donor, and the effects of additives such as activated carbon (AC), TiO2, and SiO2 powders on the cementation efficiency were investigated. Without additives, cementation efficiencies of Co2+ and Ni2+ were almost zero in both sulfate and chloride solutions, mainly because of the presence of an aluminum oxide layer (Al2O3) on an Al surface, which inhibits electron transfer from Al to the metal ions. Addition of nonconductor (SiO2) did not affect the cementation efficiencies of Co2+ and Ni2+ using Al as electron donor, while addition of (semi)conductors such as AC or TiO2 enhanced the cementation efficiencies significantly. The results of surface analysis (Auger electron spectroscopy) for the cementation products when using TiO2/Al mixture showed that Co and Ni were deposited on TiO2 particles attached on the Al surface. This result suggests that conductors such as TiO2 act as an electron pathway from Al to Co2+ and Ni2+, even when an Al oxide layer covered on an Al surface.

High-resolution neutron imaging: a new approach to characterize water in anodic aluminum oxides

During the growth of anodic Al oxide layers, water incorporates in the film and therefore influences the intrinsic properties of the oxide formed. In this study, we propose a new approach, based on the use of high-resolution neutron imaging, to visualize and quantify the water content in porous Al oxides as a function of anodizing conditions. Water in these porous films is either incorporated directly in the oxide structure (structural) and/or fills the pores (morphological). This preliminary study demonstrates that the differences in water content of porous anodic Al oxide layers are strongly related to the oxide growth parameters but interestingly cannot be directly correlated to a specific change in the amorphous oxide structure or in the pore morphology. Owing to the high sensitivity of high-resolution neutron imaging to small changes in the water content, we furthermore show that the morphological water content in Al oxides formed in sulfuric acid and in phosphoric acid is partially reversible upon heat treatment and immersion. High-resolution neutron imaging is also found to be highly sensitive to crystalline structure and disorder, allowing differentiating crystalline Al oxides based on their phases and defect content. This offers new perspectives to study the effect of the hydrogen and/or water incorporation, as well as oxide-related structural modifications, on Al oxihydroxides in relation to growth parameters, stability, functionalization, as well as properties tuning, highly relevant to surface protection and their use as templates.