Tuning Li/Ni mixing by reactive coating to boost the stability of cobalt-free Ni-rich cathode

Cobalt-free cathode materials are attractive for their high capacity and low cost,yet they still encounter issues with structural and surface instability.AlPO_(4),in particular,has garnered attention as an effective stabilizer for bulk and surface.However,the impact of interfacial reactions and elemental interdiffusion between AlPO_(4) and LiNi_(0.95)Mn_(0.05)O_(2) upon sintering on the bulk and surface remains elusive.In this study,we demonstrate that during the heat treatment process,AlPO_(4) decomposes,resulting in Al doping into the bulk of the cathode through elemental interdiffusion.Simultaneously,PO_(4)^(3-)reacts with the surface Li of material to form a Li_3PO_(4) coating,inducing lithium deficiency,thereby increasing Li/Ni mixing.The suitable Li/Ni mixing,previously overlooked in AlPO_(4) modification,plays a pivotal role in stabilizing the bulk and surface,exceeding the synergy of Al doping and Li_3PO_(4) coating.The presence of Ni^(2+)ions in the lithium layers contributes to the stabilization of the delithiated structure via a structural pillar effect.Moreover,suitable Li/Ni mixing can stabilize the lattice oxygen and electrode-electrolyte interface by increasing oxygen removal energy and reducing the overlap between the Ni^(3+/4+)e_g and O^(2-)2p orbitals.These findings offer new perspectives for the design of stable cobalt-free cathode materials.

Combined effects of ultrasonic vibration and FeCoNiCrCu coating on interfacial microstructure and mechanical properties of Al/Mg bimetal by compound casting

In this work,a new treatment method combining ultrasonic vibration with FeCoNiCrCu high entropy alloy(HEA)coating was used to prepared Al/Mg bimetal through the lost foam compound casting.The effects of composite treatment involving ultrasonic vibration and HEA coating on interfacial microstructure and mechanical properties of Al/Mg bimetal were studied.Results demonstrate that the interface thickness of the Al/Mg bimetal with composite treatment significantly decreases to only 26.99%of the thickness observed in the untreated Al/Mg bimetal.The HEA coating hinders the diffusion between Al and Mg,resulting the significant reduction in Al/Mg intermetallic compounds in the interface.The Al/Mg bimetal interface with composite treatment is composed of Al_(3)Mg_(2)and Mg_(2)Si/AlxFeCoNiCrCu+FeCoNiCrCu/δ-Mg+Al_(12)Mg_(17)eutectic structures.The interface resulting from the composite treatment has a lower hardness than that without treatment.The acoustic cavitation and acoustic streaming effects generated by ultrasonic vibration promote the diffusion of Al elements within the HEA coating,resulting in a significant improvement in the metallurgical bonding quality on the Mg side.The fracture position shifts from the Mg side of the Al/Mg bimetal only with HEA coating to the Al side with composite treatment.The shear strength of the Al/Mg bimetal increases from 32.16 MPa without treatment to 63.44 MPa with ultrasonic vibration and HEA coating,increasing by 97.26%.

Micro-aluminum powder with bi-or tri-component alloy coating as a promising catalyst:Boosting pyrolysis and combustion of ammonium perchlorate

A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.

Hot-Dip Coating of Lead-free Aluminum on Steel Substrates with Ultrasonic Vibration

Hot-dip coating has been practically employed in manufacturing zinc alloy coated steel sheets.However,it is difficult to coat aluminum alloy on a bulky steel substrate without sufficient preheating,because a rapidly solidified layer containing gas babbles is formed on a substrate surface.A variety of iron-aluminides are also formed at the interface of a steel and aluminum hot-dip coating system,which is the main difficulty in joining of steel with aluminum.Ultrasonic vibration was applied to a steel substrate during hot-dip coating of aluminum alloy to control a rapidly solidified layer and a brittle reaction layer.Hot dipping of columnar steel substrates into molten aluminum alloy （Al-2.7 mass fraction Si-4.6 mass fraction Sn） was carried out through the use of a Langevin oscillator with resonant frequency of 19.5 kHz.The application of ultrasonic vibration is quite effective to control a rapidly solidified layer and a surface oxide layer from a substrate surface by the sonocapillary effect based on a cavitation phenomenon,so that the intimate contact is achieved at the beginning of hot-dip coating.The application of ultrasonic vibration to hot-dipping is effective to control a reaction layer with less than 5 #m in thickness.An impact test exhibits that the good adhesive strength is approved in hot-dipped aluminum coatings with a thin reaction layer of approximately 5μm.

Analysis of Coating Microstructure of Hot-Dip Aluminum of Deformed Low-Carbon Steel Containing Rare Earth

The coating microstructure of hot-dip aluminum (HDA) of deformed low-carbon steel containing RE was analyzed by metallography microscopy, TEM and XRD, and the forming mechanism was also discussed. The results show that, the Fe_2Al_5 phase, on whose subcrystal boundaries, Al particles with the size of 7～30 μm existing on parallel linear are, grows a strong orientation. And the spread activation energy of Al is 155.22 kJ·mol -1. In addition, the effects of deformation on coating microstructure of hot-dip aluminum and the function of RE were preliminarily analyzed.

Influence of pyrolytic carbon coatings on complex permittivity and microwave absorbing properties of Al_2O_3 fiber woven fabrics

The pyrolytic carbon （PyC） coatings were fabricated on A1203 fiber fabrics by the method of chemical vapor deposition （CVD）. The microstructures of A1203 fibers with and without PyC coatings were characterized by SEM and Raman spectroscopy. The influence of deposition time of PyC on the DC conductivity （ad） of A1203 filaments and complex permittivity of fabrics at X band （8.2-12.4 GHz） were investigated. The values of Crd and complex permittivity increase with increasing deposition time of PyC. The electron relaxation polarization and conductance loss were supposed to be contributed to the increase of ε＇ and ε＂, respectively. In addition, the reflection loss （RL） of fabrics was calculated. The results show that the microwave absorbing properties of Al2O3 fiber fabrics can be improved by PyC coatings. The best RL results are for 60 min-deposition sample, of which the minimum value is about -40.4 dB at about 9.5 GHz and the absorbing frequency band （AFB） is about 4 GHz.

High temperature oxidation resistance and microstructure change of aluminized coating on copper substrate

The outermost coating with single phase Ni2Al3 was obtained on copper surface by electrodepositing nickel followed by slurry pack aluminizing at 800 °C for 12 h. The oxidation resistance and microstructure of the coating oxidized in ambient air at 1000 °C for 25-250 h were investigated using SEM, X-ray diffraction and optical microscope methods. The results show that the copper with single phase Ni2Al3 coating possesses the best high temperature oxidation resistance, and the mass gain of the coating is 1/15 that of pure copper and 1/2 that of nickel coating, respectively. The specimen surface after being oxidized for 25 h still comprises Ni2Al3 phase. However, when the time of oxidizing treatment increases to 50 h, the Ni Al phase is formed. It is also found that the Ni2Al3 phase completely turns into Ni Al phase after oxidizing treatment for 100 h and above. The Ni Al coating shows excellent high temperature oxidation resistance when oxidation time is 250 h.

Effects of rare earth metal addition on microstructure of hot-dip 55%Al-Zn-Si coatings

Optical microscope(OM),scanning electron microscope(SEM),energy dispersive spectrometer (EDS) and X-ray Diffraction(XRD) were used to study the effects of rare earth on the microstructural characteristics of 55%Al-Zn-1.6%Si hot -dip coatings on steel.The results of OM,SEM and EDS showed that by adding RE into the 55%Al-Zn-1.6%Si bath,the saw-toothed shape of intermetallic reaction layer of coating became smooth,and the thickness of the overlay and intermetallic reaction layer decreased.The XRD results revealed that the intermetallic reaction layer was comprised of two different regions,a bright phase closest to the steel substrate with phases of Fe_2Al_3 and a dark phase closest to the metallic coating with phases of FeAl_3/α-Fe-Al-Si.

High temperature oxidation behavior of Ti(Al,Si)_3 diffusion coating on γ-TiAl by cold spray

A Ti(Al,Si)3 diffusion coating was prepared on γ-TiAl alloy by cold sprayed Al?20Si alloy coating, followed by a heat-treatment. The isothermal and cyclic oxidation tests were conducted at 900 °C for 1000 h and 120 cycles to check the oxidation resistance of the coating. The microstructure and phase transformation of the coating before and after the oxidation were studied by SEM, XRD and EPMA. The results indicate that the diffusion coating shows good oxidation resistance. The mass gain of the diffusion coating is only a quarter of that of bare alloy. After oxidation, the diffusion coating is degraded into three layers: an inner TiAl2 layer, a two-phase intermediate layer composed of a Ti(Al,Si)3 matrix and Si-rich precipitates, and a porous layer because of the inter-diffusion between the coating and substrate.

Interface characteristics of Al_2O_3－13%TiO_2 ceramic coatings prepared by laser cladding

Al2O3-13%TiO2 （mass fraction） coatings, prepared by laser cladding on nickel-based alloy, were heated using high frequency induction sources. The coating microstructure and the interface between bond coating and ceramic coating were characterized by SEM, XRD and EDS. The results show that two-layer substructure exists in the ceramic coating： one layer evolving from fully melted region where the sintered grains grow fully; another layer resembling the liquid-phase-sintered structure consisting of three-dimensional net where the melted Al2O3 particles are embedded in the TiO2-rich matrix. The mechanism of the two-layer substructure formation is also explained in terms of the melting and flattening behavior of the powders during laser cladding processing. The spinel compounds NiAl2O4 and acicular compounds Cr2O3 are discovered in the interface between bond coating and ceramic coating. It proves that the chemical reactions in the laser cladding process will significantly enhance the coating adhesion.

Preparation of Al_2O_3/Au nano-laminated composite coatings and their oxidation resistance on stainless steel

Al2O3/Au nano-laminated composite coatings were prepared by means of magnetron sputtering. The coating was compact and comprised of nano-laminated Al2O3 and Au layers. High temperature cyclic oxidation test was employed to investigate the oxidation resistance of the composite coatings. The results revealed that the applied Al2O3/Au nano-laminated composite coatings improved the oxidation and spallation resistance of the stainless steel substrate significantly. The mechanism accounting for oxidation resistance was related with the suppression of inward oxygen diffusion and selective oxidation of Cr in the substrate. The mechanism accounting for spallation resistance was attributed to the relaxation of thermal stress by the nano-laminated structure.

Mitigating the negative catalytic effect of CuO by FAS-17 coated Al nanopowder:Isothermal ageing of Al/CuO nanothermite at 71°C and 60%relative humidity

The safety and reliability of weapon systems would be significantly affected by changes in the performance of energetic materials due to ambient temperature and humidity.Nanothermites have promising applications due to their excellent reactivity.Therefore it becomes extremely important to understand their aging and failure process in the environment before using them.Here,the aging and failure process of Al/CuO in 71°C/60%RH were investigated,and showed that CuO nanoparticles negatively catalyze Al nanopowders,resulting in rapid hydration.The anti-aging effect of FAS-17-coated Al nanopowder was also examined.The aging process of Al,Al/CuO,and Al@FAS-17/CuO in high humidity and heat environment were revealed by quasi-in situ SEM and TEM methods.Compared with the aging of pure Al,the Al nanopowder in the nanothermites strongly agglomerated with the CuO nanopowder and hydrated earlier.This may be caused by CuO catalyzed hydration of Al nanopowder.The energy release experiments showed that the performance of Al/CuO decreased rapidly and failed to ignite after 4 h of aging.In contrast,the Al@FAS-17/CuO thermite can achieve long-term stability of up to 60 h in the same environment by simple cladding of FAS-17.It is found that FAS-17 coated Al nanopowder can prevent both particle agglomeration and water erosion,which is an effective means to make nanothermites application in high humidity and heat environment.

Using EIS to evaluate anti-corrosion properties of the SiC_p/5A06 aluminium MMC treated by cerium conversion coatings

This paper evaluated the protection effect of the cerium conversion coatings on the SiCp/5A06 Al composite and the 5A06 Al alloy.Electrochemical impedance spectroscopy(EIS) was employed to examine the variation of the electrochemical variables of the samples treated and immersed in 3.5% NaCl solution at 35 °C for 1 h,which showed the enhancement of charge transfer resistance(Rt) and coating film resistance(Rc),i.e.,the corrosion resistance of the conversion coated samples was improved.The best protection ef...

INVESTIGATION ON MICROSTRUCTURE AND TRIBOLOGICAL PROPERITIES OF CORED WIRE ARC SPRAYED Al/Al _2 O_3 COATINGS

Cored wires for electric arc spraying of Al/Al 2 O 3 MMC coatings were developed, with Al 2 O 3 powder as the core material and commercial aluminium strip as the retaining sheath. The bond strength, Al 2 O 3 content, microstructure, micro-hardness and wear resistance of coatings produced by arc spraying of the cored wires were experimentally investigated and were compared with those of pure aluminum coating.

Sliding wear behavior of high velocity arc sprayed Fe-Al coating

The friction and wear behavior of Fe Al intermetallics based coating produced by high velocity arc spraying technique under dry sliding at room temperature were investigated using a ball on disc tribotester. The effect of sliding speed on friction coefficient and wear of the coating was studied. The worn surface of the coating was analyzed by scanning electron microscope (SEM) to explore sliding friction and wear mechanism. The results show that the variations of friction coefficient can be divided into three distinct steps during the trail. Both the friction coefficient and the wear of the coating increase with increased sliding speed due to accelerated crack propagation rate and lamellar structure with poor ductility of the coating. The coating surface is subjected to alternately tensile stress and compression stress during sliding wear process, and the predominant wear mechanism of the coatings appears to be brittle fracture and delamination.

Study on microstructure and properties of high velocity arc sprayed Fe_3Al intermetallic coating

Coating structural materials with Fe 3Al based intermetallics may rapidly lead to industrial application of their environment and wear resistant features. In the present study, high velocity arc spraying (HVAS) was used to in situ synthesize Fe 3Al intermetallic coating. The microstructural characterization and properties of the coating have been investigated. The microstructure was found to consist of Fe 3Al based intermetallic (D0 3 and B2) and α Fe regions together with fine oxide (α Al 2O 3) layers. TEM images of coating show that the solidified lamellae are polycrystalline and have a grain size of the order of about 150 nm , and there also exists amorphous state in some areas. It can be concluded that a very high cooling rate has been obtained during HVAS process. Moreover, the coating has relatively higher adhesion strength and microhardness, as well as lower density and porosity.

Preparation of Al2O3 nanowires on 7YSZ thermal barrier coatings against CMAS corrosion

The commonly-employed material for thermal barrier coatings(TBCs)is 7 wt.%Y2O3 ZrO2(7YSZ),generally deposited by electron beam-physical vapor deposition(EB-PVD).Due to the increasing demand for higher operating temperature in aero-derivative gas turbines,a lot of effort has been made to prevent the premature failure of columnar 7YSZ TBCs,which is induced by the microstructure degradation,sintering and spallation after the deposition of infiltrated siliceous mineral(consisting of calcium magnesium aluminum silicate(CaO MgO Al2O3 SiO2,i.e.,CMAS)).A new method called Al-modification for columnar 7YSZ TBCs against CMAS corrosion was present.The Al film was magnetron-sputtered on the surface of the columnar 7YSZ TBCs,followed by performing vacuum heat treatment of the Al-deposited TBCs.During the heat treatment,the molten Al reacted with ZrO2 to formα-Al2O3 overlay that effectively hindered CMAS infiltration.Moreover,the Al film could evaporate and re-nucleate,leading to the generation of Al2O3 nanowires,which further restrained the moving of molten CMAS.

Wetting of molten Sn-3.5Ag-0.5Cu on Ni-P(-SiC) coatings deposited on high volume faction SiC/Al composite

The wetting of molten Sn-3.5Ag-0.5Cu alloy on the Ni-P(-SiC)coated SiCp/Al substrates was investigated by electroless Ni plating process,and the microstructures of the coating and the interfacial behavior of wetting systems were analyzed.The SiC particles are evenly distributed in the coating and enveloped with Ni.No reaction layer is observed at the coating/SiCp/Al composite interfaces.The contact angle increases from^19°with the Ni-P coating to 29°,43°and 113°with the corresponding Ni-P-3SiC,Ni-P-6SiC and Ni-P-9SiC coatings,respectively.An interaction layer containing Cu,Ni,Sn and P forms at the Sn-Ag-Cu/Ni-P-(0,3,6)SiC coated SiCp/Al interfaces,and the Cu-Ni-Sn and Ni-Sn-P phases are detected in the interaction layer.Moreover,the molten Sn-Ag-Cu can penetrate into the Ni-P(-SiC)coatings through the Ni-P/SiC interface and dissolve them to contact the SiCp/Al substrate.

Structural characteristics and high-temperature tribological behaviors of laser cladded NiCoCrAlY−B_(4)C composite coatings on Ti6Al4V alloy

In order to improve the hardness and tribological performance of Ti6Al4V alloy,NiCoCrAlY-B_(4)C composite coatings with B_(4)C of 5%,10%and 15%(mass fraction)were fabricated on its surface by laser cladding(LC).The morphologies,chemical compositions and phases of obtained coatings were analyzed using scanning electronic microscope(SEM),energy dispersive spectrometer(EDS),and X-ray diffraction(XRD),respectively.The effects of B_(4)C mass fraction on the coefficient of friction(COF)and wear rate of NiCoCrAlY-B_(4)C coatings were investigated using a ball-on-disc wear tester.The results show that the NiCoCrAlY-B_(4)C coatings with different B_(4)C mass fractions are mainly composed of NiTi,NiTi_(2),α-Ti,CoO,AlB_(2),TiC,TiB and TiB_(2)phases.The COFs and wear rates of NiCoCrAlY-B_(4)C coatings decrease with the increase of B_(4)C content,which are contributed to the improvement of coating hardness by the B_(4)C addition.The wear mechanisms of NiCoCrAlY-B_(4)C coatings are changed from adhesive wear and oxidation wear to fatigue wear with the increase of B_(4)C content.

Corrosion performance and tribological behavior of diamond-like carbon based coating applied on Ni−Al−bronze alloy

The effect of diamond-like carbon(DLC)coating(fabricated by cathodic arc deposition)on mechanical properties,tribological behavior and corrosion performance of the Ni−Al−bronze(NAB)alloy was investigated.Nano-hardness and pin-on-plate test showed that DLC coating had a greater hardness compared with NAB alloy.Besides,the decrease in friction coefficient from 0.2 for NAB substrate to 0.13 for the DLC-coated sample was observed.Potentiodynamic polarization and EIS results showed that the corrosion current density decreased from 2.5μA/cm2 for bare NAB alloy to 0.14μA/cm2 for DLC-coated sample in 3.5 wt.%NaCl solution.Moreover,the charge transfer resistance at the substrate−electrolyte interface increased from 3.3 kΩ·cm2 for NAB alloy to 120.8 kΩ·cm2 for DLC-coated alloy,which indicated an increase in corrosion resistance due to the DLC coating.