Preparation and Properties of Cu-Containing High-entropy Alloy Nitride Films by Magnetron Sputtering on Titanium Alloy

Magnetron sputtering deposition with regulated Cu target power was used for depositing Cu-containing high-entropy alloy nitride(Cu-(HEA)N)films on TC4 titanium alloy substrates.The microscopic morphologies,surface compositions,and thicknesses of the films were characterized using SEM+EDS;the anti-corrosion,wear resistance and antibacterial properties of the films in simulated seawater were investigated.The experimental results show that all four Cu-(HEA)N films are uniformly dense and contained nanoparticles.The film with Cu doping come into contact with oxygen in the air to form cuprous oxide.The corrosion resistance of the(HEA)N film without Cu doping on titanium alloy is better than the films with Cu doping.The Cu-(HEA)N film with Cu target power of 16 W shows the best wear resistance and antibacterial performance,which is attributed to the fact that Cu can reduce the coefficient of friction and exacerbate corrosion,and the formation of cuprous oxide has antibacterial properties.The findings of this study provide insights for engineering applications of TC4 in the marine field.

Study on the hydrogen absorption properties of a YGdTbDyHo rare-earth high-entropy alloy

This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with the alloy elements distributed homogeneously.Upon hydrogen absorption,the phase structure of the HEA changed from a solid solution with an hexagonal-close-packed(HCP)structure to a high-entropy hydride with an faced-centered-cubic(FCC)structure without any secondary phase precipitated.The alloy demonstrated a maximum hydrogen storage capacity of 2.33 H/M(hydrogen atom/metal atom)at 723 K,with an enthalpy change(ΔH)of-141.09 kJ·mol^(-1)and an entropy change(ΔS)of-119.14 J·mol^(-1)·K^(-1).The kinetic mechanism of hydrogen absorption was hydride nucleation and growth,with an apparent activation energy(E_(a))of 20.90 kJ·mol^(-1).Without any activation,the YGdTbDyHo alloy could absorb hydrogen quickly(180 s at 923 K)with nearly no incubation period observed.The reason for the obtained value of 2.33 H/M was that the hydrogen atoms occupied both tetrahedral and octahedral interstices.These results demonstrate the potential application of HEAs as a high-capacity hydrogen storage material with a large H/M ratio,which can be used in the deuterium storage field.

Relationship between the unique microstructures and behaviors of high-entropy alloys

High-entropy alloys(HEAs),which were introduced as a pioneering concept in 2004,have captured the keen interest of nu-merous researchers.Entropy,in this context,can be perceived as representing disorder and randomness.By contrast,elemental composi-tions within alloy systems occupy specific structural sites in space,a concept referred to as structure.In accordance with Shannon entropy,structure is analogous to information.Generally,the arrangement of atoms within a material,termed its structure,plays a pivotal role in dictating its properties.In addition to expanding the array of options for alloy composites,HEAs afford ample opportunities for diverse structural designs.The profound influence of distinct structural features on the exceptional behaviors of alloys is underscored by numer-ous examples.These features include remarkably high fracture strength with excellent ductility,antiballistic capability,exceptional radi-ation resistance,and corrosion resistance.In this paper,we delve into various unique material structures and properties while elucidating the intricate relationship between structure and performance.

Effects of acetic acid on microstructure and electrochemical properties of nano cerium oxide films coated on AA7020-T6 aluminum alloy

Nano cerium oxide films were applied on AA7020-T6 aluminum alloy and the effects of acetic acid concentration on the microstructure and electrochemical properties of the coated samples were investigated by using scanning electron microscopy （SEM）, X-ray diffraction （XRD）, and potentiodynamic polarization methods. It has been found that by increasing the acetic acid/CeCl3·7H2O molar ratio, high uniform and crack-free films with well-developed grains were obtained and grain sizes of the films decreased. Elimination of cracks and decreasing grain size of the nano cerium oxide films caused corrosion resistance to increase.

Fabrication and characterization of anodic oxide films on a Ti-10V-2Fe-3Al titanium alloy

Anodic oxide films of the titanium alloy Ti-10V-2Fe-3Al in ammonium tartrate electrolyte without hydrofluoric acid or fluoride were fabricated. The morphology, components, and microstructure of the films were characterized by scanning electron microscopy （SEM）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, and Raman spectroscopy. The results showed that the films were thick, uniform, and nontransparent. Such films exhibited sedimentary morphology, with a thickness of about 3 μm, and the pore diameters of the deposits ranged from several hundred nanometers to 1.5 μm. The films were mainly titanium dioxide. Some coke-like deposits, which may contain or be changed by OH, NH, C-C, C-O, and C=O groups, were doped in the films. The films were mainly amorphous with a small amount of anatase and rutile phase.

Investigation of Formation and Inhibition Mechanism of Cerium Conversion Films on Al 2024 Alloy

To study the mechanism of formation and inhibition of Ce conversion films on Al 2024-T3 alloy, scanning microreference electrode technique (SMRE) is used to probe the potential map on Al 2024-T3 in CeCl 3 solution, the localized corrosion of Al alloy decreases with immersion time and disappears finally, which results from the competition of Cl - aggression and Ce 3+ inhibition on alloy surface. The results of X-ray photoelectron spectroscopy (XPS) indicate that the Ce conversion films consist of Al 2O 3, CeO 2 and Ce 2O 3(Ce(OH) 3), and CeO 2/Ce 2O 3 ratio decreases with the immersion time. When a critical pH for Ce(OH) 3 formation was reached, Ce(OH) 3 will precipitate on the micro cathodic area on alloy surface. Consequently, H 2O 2, the product of the catholic reaction will oxidize a part of Ce(OH) 3 to CeO 2, which appears a better corrosion resistance for Al alloys.

Preparation of Diamond-like Carbon Films on the Surface of Ti Alloy by Electro-deposition

In this paper, diamond-like carbon (DLC) films were deposited on Ti alloy by electro-deposition. DLC films were brown andcomposed of the compact grains whose diameter was about 400 nm. Examined by XPS, the main composition of the filmswas carbon. In the Raman spectrum, there were a broad peak at 1350 cm^(-1) and a broad peak at 1600 cm^(-1), which indicatedthat the films were DLC films.

Microstructure and magnetic properties of electrodeposited Gd-Co alloy films

Gd-Co alloy films were synthesized by potentiostatic electrolysis on Cu substrates in urea-acetamide-NaBr-KBr melt at 353 K. The electroreduction of Co^2＋ and Gd^3＋ was investigated by cyclic voltammetry. The reduction of Co^2＋ is an irreversible process. Gd^3＋ cannot be reduced alone, but it can be inductively co-deposited with Co^2＋. Both the Gd content and microstructure of the prepared Gd-Co alloy films can be controlled by the deposited potential. The content of Gd was analyzed using an inductively coupled plasma emission spectrometer （ICPES）, and the microstructure was observed by scanning electron micrograph （SEM）. The films were crystallized by heat-treatment at 823 K for 30 s in Ar atmosphere, and then were investigated by XRD. The hysteresis loops of the Gd-Co alloy films were measured by a vibrating sample magnetometer （VSM）. The experimental results reveal that the deposited Gd-Co alloy films are amorphous, while the annealing causes the samples to change from amorphous to polycrystalline, thus enhancing their magnetocrystalline anisotropy and coercivity. Moreover, the magnetic properties of the Gd-Co alloy films depend strongly on the Gd content.

Properties of oxide films grown on 25Cr20Ni alloy in air-H_2O and H_2-H_2O atmospheres

The oxidation kinetics,surface morphology and phase structure of oxide films grown on 25Cr20Ni alloy in air-H2O and H2-H2O atmospheres at 900 ℃ for 20 h were investigated.The anti-coking performance and resistance to carburization of the two oxide films were compared using 25Cr20Ni alloy tubes with an inner diameter of 10 mm and a length of 850 mm in a bench scale naphtha steam pyrolysis unit.The oxidation kinetics followed a parabolic law in an air-H2O atmosphere and a logarithm law in a H2-H2O atmosphere in the steady-state stage.The oxide film grown in the air-H2O atmosphere had cracks where the elements Fe and Ni were enriched and the un-cracked area was covered with octahedral-shaped MnCr2O4 spinels and Cr1.3Fe0.7O3 oxide clusters,while the oxide film grown in the H2-H2O atmosphere was intact and completely covered with dense standing blade MnCr2O4 spinels.In the pyrolysis tests,the anti-coking performance and resistance to carburization of the oxide film grown in the H2-H2O atmosphere were far better than that in the air-H2O atmosphere.The mass of coke formed in the oxide film grown in the H2-H2O atmosphere was less than 10％ of that in the air-H2O atmosphere.The Cr1.3Fe0.7O3 oxide clusters converted into Cr23C6 carbides and the cracks were filled with carbon in the oxide film grown in the air-H2O atmosphere after repeated coking and decoking tests,while the dense standing blade MnCr2O4 spinels remained unchanged in the oxide film grown in the H2-H2O atmosphere.The ethylene,propylene and butadiene yields in the pyrolysis tests were almost the same for the two oxide films.

Effect of hafnium and molybdenum addition on inclusion characteristics in Co-based dual-phase high-entropy alloys

Specific grades of high-entropy alloys(HEAs)can provide opportunities for optimizing properties toward high-temperature applications.In this work,the Co-based HEA with a chemical composition of Co_(47.5)Cr_(30)Fe_(7.5)Mn_(7.5)Ni_(7.5)(at%)was chosen.The refractory metallic elements hafnium(Hf)and molybdenum(Mo)were added in small amounts(1.5at%)because of their well-known positive effects on high-temperature properties.Inclusion characteristics were comprehensively explored by using a two-dimensional cross-sectional method and extracted by using a three-dimensional electrolytic extraction method.The results revealed that the addition of Hf can reduce Al_(2)O_(3)inclusions and lead to the formation of more stable Hf-rich inclusions as the main phase.Mo addition cannot influence the inclusion type but could influence the inclusion characteristics by affecting the physical parameters of the HEA melt.The calculated coagulation coefficient and collision rate of Al_(2)O_(3)inclusions were higher than those of HfO_(2)inclusions,but the inclusion amount played a larger role in the agglomeration behavior of HfO_(2)and Al_(2)O_(3)inclusions.The impurity level and active elements in HEAs were the crucial factors affecting inclusion formation.

Structure and corrosion behavior of FeCoCrNiMo high-entropy alloy coatings prepared by mechanical alloying and plasma spraying

FeCoCrNiMox composite powders were prepared using the mechanical alloying technique and made into high-entropy alloy(HEA)coatings with the face-centered cubic phase using plasma spraying to address the element segregation problem in HEAs and pre-pare uniform HEA coatings.Scanning electron microscopy,transmission electron microscopy,and X-ray diffractometry were employed to characterize these coatings’microstructure and phase composition.The hardness,elastic modulus,and fracture toughness of coatings were tested,and the corrosion resistance was analyzed in simulated seawater.Results show that the hardness of the coating is HV0.1606.15,the modulus of elasticity is 128.42 GPa,and the fracture toughness is 43.98 MPa·m^(1/2).The corrosion potential of the coating in 3.5wt%NaCl solution is-0.49 V,and the corrosion current density is 1.2×10^(−6)A/cm^(2).The electrochemical system comprises three parts:the electrolyte,the adsorption and metallic oxide films produced during immersion,and the FeCoNiCrMo HEA coating.Over in-creasingly long periods,the corrosion reaction rate increases first and then decreases,the corrosion product film comprising metal oxides reaches a dynamic balance between formation and dissolution,and the internal reaction of the coating declines.

Selective Hydrodeoxygenation of Lignin-Derived Vanillin via Hetero-Structured High-Entropy Alloy/Oxide Catalysts

The chemoselective hydrodeoxygenation of natural lignocellulosic materials plays a crucial role in converting biomass into value-added chemicals.Yet their complex molecular structures often require multiple active sites synergy for effective activation and achieving high chemoselectivity.Herein,it is reported that a high-entropy alloy(HEA)on high-entropy oxide(HEO)hetero-structured catalyst for highly active,chemoselective,and robust vanillin hydrodeoxygenation.The heterogenous HEA/HEO catalysts were prepared by thermal reduction of senary HEOs(NiZnCuFeAlZrO_(x)),where exsolvable metals(e.g.,Ni,Zn,Cu)in situ emerged and formed randomly dispersed HEA nanoparticles anchoring on the HEO matrix.This catalyst exhibits excellent catalytic performance:100%conversion of vanillin and 95%selectivity toward high-value 2-methyl-4 methoxy phenol at low temperature of 120℃,which were attributed to the synergistic effect among HEO matrix(with abundant oxygen vacancies),anchored HEA nanoparticles(having excellent hydrogenolysis capability),and their intimate hetero-interfaces(showing strong electron transferring effect).Therefore,our work reported the successful construction of HEA/HEO heterogeneous catalysts and their superior multifunctionality in biomass conversion,which could shed light on catalyst design for many important reactions that are complex and require multifunctional active sites.

Magnetic Properties and Heat-Treatment of Electrodeposited Sm-Co Alloy Films

Dense, adhesive and uniform Sm-Co alloy films were prepared by potentiostatic electrolysis on copper substrates in urea-acetamide-NaBr-KBr melt at 353 K, which were observed by SEM. The electroreduction of Co2+ and Sm3+ was investigated by cyclic voltammetry. The reduction of Co2+ is an irreversible process. Sm3+ can not be reduced alone, but Sm-Co can be co-deposited by induced deposition. The films could be crystallized by heat-treatment at different temperature from 723 to 923 K under Ar atmosphere. The annealed time was chosen as 30 s. The phases of deposited and annealed films were investigated by XRD. The content of Sm was analyzed by Inductive Coupled Plasma Emission Spectrometer (ICPES). The hysteresis loops of the Sm-Co alloy films have been measured by Vibrating Sample Magnetometer (VSM). The experimental results reveal that, the heat-treatment has important influence on coercive field Hc and remanent squareness S of Sm-Co alloy films; the deposited Sm-Co alloy films are amorphous, while the annealed those become polycrystalline; in addition, the magnetocrystalline anisotropy and preferring orientation of films depend strongly on the contents of crystal phases.

Accelerated intermetallic phase amorphization in a Mg-based high-entropy alloy powder

We describe a novel mechanism for the synthesis of a stable high-entropy alloy powder from an otherwise immiscible Mg-Ti rich metallic mixture by employing high-energy mechanical milling.The presented methodology expedites the synthesis of amorphous alloy powder by strategically injecting entropic disorder through the inclusion of multi-principal elements in the alloy composition.Predictions from first principles and materials theory corroborate the results from microscopic characterizations that reveal a transition of the amorphous phase from a precursor intermetallic structure.This transformation,characterized by the emergence of antisite disorder,lattice expansion,and the presence of nanograin boundaries,signifies a departure from the precursor intermetallic structure.Additionally,this phase transformation is accelerated by the presence of multiple principal elements that induce severe lattice distortion and a higher configurational entropy.The atomic size mismatch of the dissimilar elements present in the alloy produces a stable amorphous phase that resists reverting to an ordered lattice even on annealing.

Utlra-fast hydrolysis performance of MgH_(2) catalyzed by Ti-Zr-Fe-Mn-Cr-V high-entropy alloys

Hydrogen energy is one of the ideal energy alternatives and the upstream of the hydrogen industry chain is hydrogen production,which can be achieved via the reaction of inorganic materials with water,known as hydrolysis.Among inorganic materials,the high hydrogen capacity for hydrolysis of MgH_(2)(15.2 wt%)makes it a promising material for hydrogen production via hydrolysis.However,the dense Mg(OH)_(2) passivation layer will block the reaction between MgH_(2) and the solution,resulting in low hydrogen yield and sluggish hydrolysis kinetics.In this work,the hydrogenyield and hydrogen generation rate of MgH_(2) are considerably enhanced by adding Ti-Zr-Fe-Mn-Cr-V high-entropy alloys(HEAs) for the first time.In particular.the MgH_(2)-3 wt% TiZrFe_(1.5)MnCrV_(0.5)(labelled as MgH_(2)-3 wt% Fe_(1.5)) composite releases 1526.70 mL/g H_(2) within 5 min at 40℃,and the final hydrolysis conversion rate reaches 95.62% within 10 min.The mean hydrogen generation rate of the MgH_(2)-3 wt% Fe_(1.5) composite is 289.16 mL/g/min,which is 2.38 times faster than that of pure MgH_(2).Meanwhile,the activation energy of the MgH_(2)-3 wt% Fe_(1.5) composite is calculated to be 12.53 kJ/mol. The density functional theory(DFT) calculation reveals that the addition of HEAs weakens the Mg-H bonds and accelerates the electron transfer between MgH_(2) and HEAs,Combined with the cocktail effect of HEAs as well as the formation of more interfaces and micro protocells,the hydrolysis performance of MgH_(2) is considerably improved.This work provides an appealing prospect for real-time hydrogen supply and offers a new effective strategy for improving the hydrolysis performance of MgH_(2).

Comprehensive insights into recent innovations:Magnesium-inclusive high-entropy alloys

This review focuses on thermodynamic and physical parameters,synthesis methods,and reported phases of Magnesium(Mg)containing high-entropy alloys(HEAs).Statistical data of publications concerning Mg-containing HEAs were collected and analyzed.Data on the chemical elements included in Mg-containing HEAs,their theoretical end experimental densities,thermodynamic parameters,physical parameters,fabricated techniques and reported phases were also collected and discussed.On the basis of this information,a new classification for HEAs was proposed.It is also shown that the existing thermodynamic parameters cannot accurately predict the formation of a single phase solid solution for Mg-containing HEAs.The physical parameters of Mg-containing HEAs are within a wide range,and most of the synthesized Mg-containing HEAs have a complex multiphase structure.

Surface Analysis of Chemical Stripping Titanium Alloy Oxide Films

The chemical stripping method of titanium alloy oxide films was studied. An environment friendly solution hydrogen peroxide and sodium hydroxide without hydrofluoric acid or fluoride were used to strip the oxide films. The morphologies of the surface and cross-section of the oxide films before and after the films stripping were characterized by using scanning electron microscopy （SEM）. The microstructure and chemical compositions of the oxide films before and after the films stripping were investigated by using Raman spectroscopy （Raman） and X-ray photoelectron spectroscopy （XPS）. It was shown that the thickness of the oxide film was in the range of 5-6 μm. The oxide films were stripped for 2 to 8 min in the solution. Moreover, the effect of the stripping time on the efficiency of the film stripping was investigated, and the optimum stripping time was between 6-8 min. When the stripping solution completely dissolved the whole film, the α/β microstructure of the titanium alloy Ti-10V-2Fe-3Al was partly revealed. The stripping mechanism was discussed in terms of the dissolution of film delamination. The hydrogen peroxide had a significant effect on the dissolution of the titanium alloy anodic oxide film. The feasibility of the dissolution reaction also was evaluated.

Evolution of helium bubbles in FeCoNiCr-based high-entropy alloys containing γ′ nanoprecipitates

A series of high-entropy alloys(HEAs) containing nanoprecipitates of varying sizes is successfully prepared by a non-consuming vacuum arc melting method.In order to study the irradiation evolution of helium bubbles in the FeCoNiCrbased HE As with γ' precipitates,these samples are irradiated by 100-keV helium ions with a fluence of 5 × 10^(20) ions/m^(2) at 293 K and 673 K,respectively.And the samples irradiated at room temperature are annealed at different temperatures to examine the diffusion behavior of helium bubbles.Transmission electron microscope(TEM) is employed to characterize the structural morphology of precipitated nanoparticles and the evolution of helium bubbles.Experimental results reveal that nanosized,spherical,dispersed,coherent,and ordered L1_(2)-type Ni_(3)Ti γ' precipitations are introduced into FeCoNiCr(Ni_(3)Ti)_(0.1) HEAs by means of ageing treatments at temperatures between 1073 K and 1123 K.Under the ageing treatment conditions adopted in this work,γ' nanoparticles are precipitated in FeCoNiCr(Ni_(3)Ti)_(0.1) HE As,with average diameters of 15.80 nm,37.09 nm,and 62.50 nm,respectively.The average sizes of helium bubbles observed in samples after 673-K irradiation are 1.46 nm,1.65 nm,and 1.58 nm,respectively.The improvement in the irradiation resistance of FeCoNiCr(Ni_(3)Ti)_(0.1) HEAs is evidenced by the diminution in bubbles size.Furthermore,the FeCoNiCr(Ni_(3)Ti)_(0.1) HEAs containing γ' precipitates of 15.8 nm exhibits the minimum size and density of helium bubbles,which can be ascribed to the considerable helium trapping effects of heterogeneous coherent phase boundaries.Subsequently,annealing experiments conducted after 293-K irradiation indicate that HEAs containing precipitated phases exhibits smaller apparent activation energy(E_(a)) for helium bubbles,resulting in larger helium bubble size.This study provides guidance for improving the irradiation resistance of L1_(2)-strengthened high-entropy alloy.

High-entropy alloys in thermoelectric application:A selective review

Since the superior mechanical,chemical and physical properties of high-entropy alloys(HEAs)were discovered,they have gradually become new emerging candidates for renewable energy applications.This review presents the novel applications of HEAs in thermoelectric energy conversion.Firstly,the basic concepts and structural properties of HEAs are introduced.Then,we discuss a number of promising thermoelectric materials based on HEAs.Finally,the conclusion and outlook are presented.This article presents an advanced understanding of the thermoelectric properties of HEAs,which provides new opportunities for promoting their applications in renewable energy.

Effect of Mn content on microstructure and properties of AlCrCuFeMnx high-entropy alloy

AlCrCuFeMnx(x=0,0.5,1,1.5,and 2)high-entropy alloys were prepared using the vacuum arc melting technology.The microstructure and mechanical properties of AlCrCuFeMnxwere analyzed and tested by XRD,SEM,TEM,nanoindentation,and electronic universal testing.The results indicate that the AlCrCuFeMnxhigh-entropy alloy exhibits a dendritic structure,consisting of dendrites with a BCC structure,interdendrite regions with an FCC structure,and precipitates with an ordered BCC structure that form within the dendrite.Manganese(Mn)has a strong affinity for dendritic,interdendritic,and precipitate structures,allowing it to easily enter these areas.With an increase in Mn content,the size of the precipitated nanoparticles in the dendritic region initially increases and then decreases.Similarly,the area fraction initially decreases and then increases.Additionally,the alloy’s strength and wear resistance decrease,while its plasticity increases.The Al Cr Cu Fe Mn1.5alloy boasts excellent mechanical properties,including a hardness of 360 HV and a wear rate of 2.4×10^(-5)mm^(3)·N^(-1)·mm^(-1).It also exhibits impressive yield strength,compressive strength,and deformation rates of 960 MPa,1,700 MPa,and 27.5%,respectively.