Construction of an outstanding HMCF/PEEK interface by cathodic electrophoretic deposition of PEI/MXene composite nanoparticles with excellent stability to enhance the mechanical properties of the composite materials

The construction of C-C bonds is a pivotal transformation in organic synthesis. Traditional Ullmann type and Hurtley reactions for constructing C(sp3)-C(sp2) bonds rely on organometallic reagents or substrates with active methylene units. These requirements significantly limit their practical applicability. Herein, employing two readily available organic halides, we report a ligand-enabled, electrochemical copper-catalyzed cross-electrophile coupling. Although Cu is the first metal reported for C-C bond construction, cross-electrophile coupling nowadays is dominated by Ni. This work demonstrates that efficient cross-electrophile coupling can be realized by electrochemical Cu catalysis. Our protocol is applicable to a wide range of propargyl bromides and (hetero)aryl iodides or bromides, delivering the desired products in good yields with high cross-selectivity. The use of an orthodimethylamine-substituted diamine ligand is crucial for promoting the reaction and suppressing cathodic Cu deposition. We attribute this effect to an intramolecular H···N H-bonding, which facilitates hyperconjugation between the NMe2 moiety and the nitrogen atom coordinated to the Cu center. Mechanistic studies indicate that the reaction follows a radical pathway, contrasting with the SN2 pathway reported previously. This work establishes a foundation for electrochemical Cu-catalyzed cross-electrophile coupling and provides a new paradigm for Cu-catalyzed C-C bond formation via radical intermediates.

To improve the low deposition rate of atomic layer deposition (ALD), we introduced filtered cathodic vacuum arc (FCVA) technology for the high-rate deposition of Al2O3 films. The FCVA-Al2O3 process achieved a deposition rate of 15 nm/min, which is approximately an order of magnitude higher than that of conventional ALD. This process does not involve hydrogen, preventing hydrogen ion penetration and thereby ensuring the high stability of the oxide TFT backplane. FCVA-Al2O3 films were integrated with inkjet-printed (IJP) organic layers to form a hybrid thin-film encapsulation (TFE) structure for OLEDs. The resulting laminated encapsulation exhibited excellent water vapor barrier properties (WVTR, Water Vapor Transmission Rate of 1.2 × 10-4 g/m2/day), demonstrating the great potential of FCVA for packaging high-throughput and high-performance flexible electronics. In addition to evaluating barrier properties (surface roughness, residual stress, and WVTR) to assess the suitability of TFE, the impact of FCVA technology was assessed via oxide thin-film transistor (TFT) electrical performance and OLED device reliability tests. The electrical properties of oxide TFTs show no significant degradation post-encapsulation, while OLED performance, despite a slight increase in current efficiency, remains effectively unchanged. Additionally, the lifetime of OLED devices reached 300 h under accelerated aging conditions (85 °C, 85% relative humidity), which is nearly twice that of devices without FCVA-Al2O3 encapsulation.

The sluggish kinetics and poor stability of the oxygen reduction reaction (ORR) remain the primary bottleneck for achieving high performance in protonic ceramic fuel cells (PCFCs) at intermediate temperatures (400-650°C). In this work, a Pr-based nanocomposite cathode comprised of simple perovskite phase (PrNi0.7Co0.3O3-δ) and Ruddlesden-Popper phase (Co-doped Pr4Ni3O10+δ) is developed. Although PrNi0.7Co0.3O3-δ solely stands as a good cathode with facile proton transfer, combining the superior catalytic activity against oxygen on the Ruddlesden-Popper phase boosts the ORR performance further. The designed nanocomposite cathode outperforms the simple perovskite cathode, attributed to enhanced oxygen absorption and surface diffusion with the Ruddlesden-Popper phase. A precursor-based cathode deposition technique is also developed to achieve cathode grain sizes of ∼100nm. A single cell with the nanocomposite cathode delivers a peak power density of 1.38W cm-2 at 650°C, among the highest in reported PCFCs with Pr-based cathodes, with a small degradation rate of 0.145mV h-1 during 250h stability test. Further investigation of cathode-electrolyte interface revealed interfacial PrO2 phase formation, promoted by abundant Pr6O11 in the nanocomposite precursor powder, thereby improving both ohmic resistance and stability. These findings highlight the effectiveness of the nanocomposite cathode and underscore its advantages on interfacial properties.

Efficient removal of lanthanide elements during dry processing of spent nuclear fuel is a critical step. Owing to their high neutron absorption cross-section, these lanthanide elements hinder the transmutation of actinide elements. The conventional molten salt electrolysis method for lanthanide extraction suffers from declining efficiency in later stages and high molten salt costs. To address these challenges, this research puts forward a two-pronged approach combining cathode application with elevated-temperature absorption to effectively extract lanthanides and decontaminate radioactive molten salts. Electrochemical analysis via CV, SWV, and OCP measurements was performed on tin electrodes with target ions. Electrolytic extraction using liquid tin as the cathode demonstrated high efficiency: steady 50 mA electrolysis yielded 96.57% average terbium recovery, while constant potential electrolysis at -1.30 V reached 97.32%. Subsequently, based on these electrolysis experiments, molecular sieves were employed to effectively remove terbium ions, achieving a maximum removal rate exceeding 96.47% within the temperature range of 798 to 873 K. For multicomponent lanthanide systems (comprising holmium(III), neodymium(III), praseodymium(III), terbium(III), and thulium(III)), the molecular sieves maintained high removal rates (ranging from 92.41 to 97.64%). Consequently, the synergistic effect of cathode deposition and high-temperature adsorption resulted in a total terbium removal rate of up to 99.91%, while enabling the recovery of LiCl-KCl molten salt and minimizing secondary waste. This strategy effectively mitigates the high cost and low efficiency issues associated with traditional methods, offering an economically viable, efficient, and eco-friendly alternative for separating lanthanide elements in dry spent nuclear fuel processing.

Cathodic arc deposition of TiAlN coatings and its influence on their physical and mechanical properties, structure and phase composition

This study presents a comprehensive performance analysis of aluminum titanium nitride (AlTiN) and aluminum chromium nitride (AlCrN) coatings applied to stainless steel 316L (SS316L) stainless steel substrates, evaluating their potential as metallic bipolar plates in proton exchange membrane fuel cells (PEMFCs). The coatings were deposited using the cathodic arc physical vapor deposition (CA-PVD) technique. Extensive material characterization revealed significant improvements in key properties, including a reduction in interfacial contact. The corrosion resistance of AlTiN- and AlCrN-coated SS316L bipolar plates was evaluated under simulated PEMFC conditions. Both coatings exhibited corrosion current densities below the US DOE 2025 target of 1 µA cm−2, confirming excellent electrochemical stability, alongside increased hydrophobicity. Adhesion tests confirmed the stability of both coatings, achieving a top rating of grade 5B. Single-cell fuel cell testing demonstrated a notable improvement in performance, with AlTiN-coated plates exhibiting an 18.59% increase in peak power density 12.452 mW per cm2 compared to uncoated SS316L plates at 10.5 mW per cm2, outperforming the AlCrN-coated plates. These findings highlight AlTiN as a promising coating material for enhancing the durability and efficiency of PEMFCs, suggesting potential for further optimization through advanced membrane electrode assembly MEA configurations.

Improvement in surface properties of AISI-5160 steel by transition metal (Nb, V) nitride coating through cathodic cage plasma deposition

Cathodic Cage Plasma Deposition of Ag/Porous Silicon as a Scalable Route To SERS Substrates

This review summarizes the development of cathodic cage plasma nitriding (CCPN) and cathodic cage plasma deposition (CCPD) techniques. CCPN was introduced to eliminate issues in direct current plasma nitriding (DCPN), such as the edge effect, by isolating the sample at a floating potential and using radiative heating. The process was further adapted for CCPD, in which the cage serves as a sputtering target (e.g., Ti, graphite, Mo, Hastelloy) for the deposition of ceramic and metallic films. Combining nitriding pretreatment with CCPD resulted in duplex treatments that establish a hardness gradient and enhance film adhesion. The most recent advance is cathodic cylinder plasma deposition (CCyPD), which employs compacted powder targets (such as MoS2 or metal oxides) for composite film deposition and in situ oxide reduction. The review traces the evolution from process improvement to a versatile platform for surface engineering.

Abstract To enhance the utilization of spent fuel and achieve nuclear fuel recycling, the extraction of rare earth element thulium (Tm) was studied using electrorefining methods. The electrodeposition processes of Tm(III) and Cu(II) ions on a W electrode, as well as Tm(III) ions on a Cu electrode, were examined using open-circuit chronopotentiometry (OCP), square wave voltammetry (SWV) and cyclic voltammetry (CV) in a LiCl–KCl molten salt environment. The process of alloy formation and dissolution of Tm on the cathode was studied using open-circuit chronopotentiometry. The changes in entropy and enthalpy of the formed Cu 5 Tm alloy were computed as 205.05 kJ·mol⁻¹ and -30.92 J·mol⁻¹·K⁻¹ correspondingly. Additionally, the cathode deposits were characterized and investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). It was found that the extraction rate of Tm(III) by constant potential electrolysis averages 94.35 % based on the ICP-OES measurements of the TmCl 3 concentration in the molten salt prior to and following electrolysis. Therefore, electrolytic refining through the dry reprocessing of spent fuel can effectively remove key fission products from the spent fuel.

Abstract This work provides a quantitative analysis of what it would take to fully evaporate copper macroparticles embedded in a cathodic arc plasma flow. This analysis is important for the justification of efforts to develop an evaporation scheme based on adding an electron beam. We want to explore if this approach could be an alternative to conventional plasma filtering to obtain macroparticle-free plasma from a cathodic arc plasma source. If successful, cathodic arc plasma deposition could be extended from a popular technology for hard and decorative coatings to much more demanding coatings applications, for example in microelectronics. Here, we study the feasibility and economical implication of evaporating micrometer-sized macroparticles on length and time scales typical for cathodic arc deposition systems. We show by analytical modeling that macroparticles with a radius ⩽1 µ m can be completely evaporated in a plasma of density 10 16 m −3 when using an electron beam of at least 3 keV and a beam electron density of at least 10 14 m −3 . While the theoretical opportunity is shown, we acknowledge the significant practical and economic challenges in the practical implementation of the approach.

The inhomogeneity and droplet related defects of cathodic arc deposition and lower ion density of magnetron sputtering-based tool coatings are the challenges that lowers coating quality. The present study carries two types of tool coatings in which one set of cutting inserts are coated with single layer conventional cathodic arc evaporation while the other set is coated with bimodal coating (arc and sputtering). The bimodal coating utilises an arc current of 80 A for the adhesive base layer and sputtering current of 500 mA for the surface refinement layer. SEM micrographs and atomic force microscopy confirmed that the bimodal coating significantly reduced the droplet density as well as improved the surface uniformity of arc deposited coating (84.9% reduction in R t value). XRD plots reveal the formation of the nanocrystalline cubic structure of TiN. The crystallite sizes were analysed by Scherrer equation which were 12.4 and 14.3 nm for single layer and bimodal coating respectively. The bimodal coating showed a 7.3% enhancement in nano-hardness confirmed its superior performance. During the end milling of Nimonic 90 under constant machining parameters of 75 m/min cutting speed, 100 mm/min feed, and 0.05 mm axial depth of cut under a 5 bar compressed air cutting environment, the bimodal coated tool reduced the cutting forces, surface roughness, and cutting temperature by 45.26%, 34.24%, and 25.93% respectively compared with cathodic arc coating. These findings highlight that combining arc evaporation with sputtering effectively enhances coating quality for advanced machining applications.

This material presents the research of AlTiN coating properties, deposited at low temperature by cathodic arc physical vapor deposition technology. As well as evolutionary development of coating when is added Cr element to it, or creating multilayer structure adding a CrN as internal layer on it. Each of these steps results in increasing with almost 80% of coating resistance to plastic deformation and a huge reduction in the wear rate of the resulting coating.

The possibility of electrochemically forming highly filled composite electrochemical coatings Ni-Al with an atomic ratio of components close to the optimal (1:1) from an electrolyte based on a deep eutectic solvent of choline chloride urea is demonstrated. Aluminum was introduced into the electrolyte in the form of ASD-4 powder. The aluminum additive in such an electrolyte is resistant to oxidation over a long period of time, which ensures the stability of the Ni-Al coating composition. Data on the elemental and phase composition of the Ni-Al electrochemical coatings indicate the potential for their use as high-energy composites. Aluminum is included in the coatings primarily in a metallic, unoxidized state. Both metals are contained in the coatings primarily in the elemental state; intermetallic compounds of nickel and aluminum are not detected. Carbon and oxygen impurities detected in the Ni-Al coatings are associated with the inclusion of components of the deep eutectic solvent and/or products of their electrochemical transformation, in particular, in the form of nickel carbide, in the cathode deposit.

This study investigates the influence of long-chain quaternary ammonium surfactant cetyltrimethylammonium bromide (CTAB) on the performance of copper foil, including tensile strength and aqueous wettability. The addition of CTAB leads to an average ultrahigh tensile strength of 711 MPa and elongation of 7.32% of copper foil. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Electron backscatter diffraction (EBSD) analyses revealed that CTAB significantly reduced copper grain size and improved surface uniformity. Electrochemical tests confirmed the suppressing effect of CTAB on cathodic copper deposition. Density functional theory (DFT) calculation and in situ infrared spectroscopy (in situ FTIR) analysis show that adsorption of CTAB on the copper substrate suppresses the electroreduction of Cu2+ to Cu and increases the cathodic polarization, thus effectively refining the grain structure. This work validates CTAB as a potent suppressor for improving the mechanical properties and wettability of copper foils.

Highly efficient separation of lanthanides and recycling of radioactive molten salts achieved by coupling cathodic deposition with 4A molecular sieve adsorption

Metal-organic frameworks (MOFs) are a class of porous materials which are composited of inorganic metal nodes and organic linkers.1 MOF films have garnered significant interest from researchers due to their high surface area, ordered nanosized pore structures, and customizable physicochemical properties. These features make them highly promising for a range of applications, including molecular sieving, catalysis, sensing, and more.2 However, most of the existing methods (e.g., solvothermal synthesis, chemical vapor deposition, layer-by-layer deposition, and interfacial polymerization synthesis) for MOF film preparation are far from satisfactory due to issues like complex fabrication steps, high cost, and lack of film quality control. Cathodic deposition is an emerging technique for MOF film preparation, featuring a reduction reaction-triggered deprotonation of organic ligands on substrate surface. Because of its mild conditions, simple operation, and the possibility of obtaining defect-free MOF films, the cathodic deposition of MOF films is recognized as a promising technique for continuous MOF film preparation. Nevertheless, this technique is still in its early stages and faces several challenges. For example, during the cathodic deposition of some typical MOFs like HKUST-1 and MOF-5, unwanted metal co-deposition can occur, resulting in impurities in the obtained MOF films. Additionally, previous studies have shown that cathodic deposition is ineffective on poorly conductive polymer membranes, limiting its substrate compatibility. Also, the range of MOF species that can be cathodically deposited is very limited, which significantly restricts its practical applications. This contribution will introduce the solutions of these issues existing in the cathodic deposition of MOF films. The possible applications of the cathodically deposited MOF films will also be covered. Zhou, H.-C.; Long, J. R.; Yaghi, O. M., Introduction to metal–organic frameworks. Chemical reviews 2012, 112 (2), 673-674.Shi, X.; Shan, Y.; Du, M.; Pang, H., Synthesis and application of metal-organic framework films. Coordination Chemistry Reviews 2021, 444, 214060.

Relative activities of rare earths in molten LiCl-KCl are important for predicting partitioning of rare earth fission products during electrochemical processing of used nuclear fuel. In such processing, metallic spent fuel is loaded into an anode basket and polarized to electrorefine U or U/TRU. TRU is an acronym for transuranic actinides. The electrolyte is commonly comprised on eutectic LiCl-KCl with 5-10 wt% UCl3. Given this electrolyte composition, cathodic deposition first favors U then TRU then rare earth metals. The precise sequence of deposition is dependent upon equilibrium potentials, which are unique for each metal. The Nernst equation can be used to calculate the equilibrium potential for each metal under the condition in which deposition of the metal has initiated. For each metal, the Nernst equation requires a standard potential, activity of the metal in the salt as a chloride, and activity of the metal in its reduced state. Even under the most simplifying case in which each metal reduces to a pure solid with activity of one, there is insufficient data from the literature to build a verified order of rare earth metal activity. Some reported potentials are reported as apparent standard potentials, meaning that they assume constant equilibrium potential as metal chloride concentration approaches zero. However, Bagri and Simpson reported that equilibrium potentials for rare earth chloride salts do not in fact approach a constant value in the direction of infinite dilution. In a series of variable concentration experiments, Gd/Gd3+, Nd/Nd3+, Ce/Ce3+, and La/La3+ were compared in LiCl-KCl at 773 K. The observed sequence of activity was LaCl3 > CeCl3 > NdCl3 > GdCl3. But that sequence disagrees with standard apparent reduction potentials reported by Zhang (LaCl3 > NdCl3 > CeCl3 > GdCl3). Given that the potential differences are very small and reference electrodes were used in the measurements made by Bagri and Simpson, a new experiment was devised and executed to yield a more definitive activity sequence for these key rare earth metals. The experiment does not involve use of a reference electrode. Rather, it involves relative potential measurements between Gd, Nd, Ce, and La metal immersed in eutectic LiCl-KCl at temperatures ranging from 723 to 823 K. The salt was initially spiked with a small concentration of LaCl3 and allowed to equilibrate. Salt samples were taken and concentrations of Gd, Nd, Ce, and La were measured using ICP-MS. Results of these experiments will be reported and compared to calculated standard potentials based on standard state Gibb’s free energy of formation for each rare earth chloride. These results should definitively establish the order or rare earth activity in LiCl-KCl, eliminating error induced by reference electrodes.

ZIF-L, possessing a unique two-dimensional (2D) structure and cushion-shaped sub-nanometer windows, holds great promise for high-performance gas separations. However, preparing ZIF-L films remains challenging due to their metastable nature. Herein, we report the cathodic deposition of thin ZIF-L films. By integrating comprehensive experimental and computational studies, we uncovered that the metal node and ligand concentrations on the working electrode surface are crucial to the generation of ZIF-L films. Based on this finding, we developed a stragegy to regulate the surface metal ion and ligand concentrations, and ultimately achieved the cathodic deposition of ZIF-L thin films. With polydimethylsiloxane (PDMS) post-modification, the electrochemically deposited ZIF-L films on Pt-coated anodized alumina oxide substrate exhibit outstanding gas separation performance, achieving a remarkable H₂/N₂ selectivity and a high H₂ permeance, comparable to the state-of-the-art membranes in literature. This study not only introduces a new method to prepare ZIF-L films but also presents a general strategy to modulate the surface concentrations of metal nodes and ligands in the cathodic depostion of MOF films.