Investigation of a novel self-sealing pore micro-arc oxidation film on AM60 magnesium alloy

Micro-arc oxidation(MAO)is one of the promising methods to improve the corrosion resistance of magnesium alloys.However,there are plenty of micro-pores in the traditional MAO films,deteriorating their protection property.A novel self-sealing pore MAO film was developed in this paper.The morphologies and chemical composition of the film were detected by scanning electron microscopy(SEM)and energy dispersive X-ray spectroscopy(EDX).The corrosion behavior was investigated by electrochemical and salt spray tests.The possible film formation and corrosion mechanisms were proposed.The self-sealing pore film presents a blue appearance.Most of the micro-pores in the surface of the film are sealed during the film formation process.The chemical composition of the film mainly contains Mg,O,Ti,F and P.The self-sealing pore film exhibits better corrosion resistance compared with the traditional silicate film.Especially,the self-sealing pore film keeps intact after salt spray test for 2000 h,which can be attributed to its high compactness.

Structure Analysis of Oxidation Film of Ignition-Inhibition AZ91D Magnesium Alloy Added with Cerium

The effect of cerium on ignition temperature of AZ91D magnesium alloy was studie d. By the addition of cerium of 1%, the ignition temperature is raised by 180 ℃ , s o the magnesium alloy added with cerium can be melted in air. The burning temper ature increases with the increasing of cerium. The structure and chemical compos itions of the surface oxide film were investigated by XRD and Auger electron spe ctrometry(AES). The results of XRD indicate that the oxide film of the surface o f ignition-inhibition magnesium alloy can change from loose structure of simple magnesia to compact composite structure consisting of magnesia, cerium oxide, M g17 A112 and aluminum oxide, which has excellent ignition-inhibition effect. AE S depth profile analysis shows that the oxide film can be divided into three lay ers. The outside layer is mainly made up of magnesia, the middle layer, which co nsists of cerium oxide, magnesia, and aluminum oxide, is compound and compact. T hermodynamic analysis indicates that the structure of the surface oxide film is accordant to the change of free energy and high vapor pressure of magnesium.

Oxidation behavior of 4774DD1 Ni-based single-crystal superalloy at 980℃ in air

The oxidation behavior of a novel Ni-based single-crystal 4774DD1 superalloy for industrial gas turbine applications was investigated by the isothermal oxidation at 980℃ and discontinuous oxidation weight gain methods.The phase constitution and morphology of surface oxides and the characteristics of the crosssection oxide film were analyzed by XRD,SEM and EDS.Results show that the oxidation kinetics of the 4774DD1 superalloy follows the cubic law,indicating its weak oxidation resistance at this temperature.As the oxidation time increases,the composition of the oxide film evolves as following:One layer consisting of a bottom Al_(2)O_(3)sublayer and an upper(Al_(2)O_(3)+NiO)mixture sublayer after oxidized for 25 h.Then,two layers composed of an outermost small NiO discontinuous grain layer and an internal layer for 75 h.This internal layer is consisted of the bottom Al_(2)O_(3)sublayer,an intermediate narrow CrTaO_(4)sublayer,and an upper(Al_(2)O_(3)+NiO)mixture sublayer.Also two layers comprising an outermost relative continuous NiO layer with large grain size and an internal layer as the oxidation time increases to 125 h.This internal layer is composed of the upper(Al_(2)O_(3)+NiO)mixture sublayer,an intermediate continuous(CrTaO_(4)+NiWO_(4))mixture sublayer,and a bottom Al_(2)O_(3)sublayer.Finally,three layers consisting of an outermost(NiAl2O_(4)+NiCr2O_(4))mixture layer,an intermediate(CrTaO_(4)+NiWO_(4))mixture layer,and a bottom Al_(2)O_(3)layer for 200 h.

Nickel-free sealing technology for anodic oxidation film of aluminum alloy at room temperature

Different additives were added into the potassium fluorozirconate solution to prepare different nickelfree sealing reagents,with which the anodic oxidation film of aluminum alloy was sealed at room temperature.The phosphor chromic acid weight loss method was used to evaluate the sealing effects.Using electron scanning microscopy(SEM),the surface and cross-sectional micromorphologies of the anodic oxidation films sealed by different fluorozirconate sealants were observed.The position and state of zirconium element distribution in the film hole were investigated by the further quantitative and distribution analysis of Zr element.This study provides an experimental evidence for the theoretical studies of fluorozirconate-sealed anodic oxidation films.It is shown that the fluorozirconate has good sealing effects and has a wide prospect for sealing the aluminum alloy samples.Its products were highly corrosion resistant,and were filled in the openings of the micropores in the oxide film.

Preparation and crystalline phase of a TiO_2 porous film by anodic oxidation

Anatase titanium dioxide is an active photocatalyst, but it is difficult to immobilize on the substrate. A crystalline TiO2 porous film was prepared directly on the surface of pure titanium by anodic oxidation in this work. Constant voltage and constant current anodic oxidation were adopted with sulphuric acid used as the electrolyte, pure titanium as the anode and copper as the cathode. The morphology and structure of the porous film on the substrate were analyzed with the aid of Field Emission Scanning Electron Microscopy （FESEM） and X-ray Diffraction （XRD）. The effects of the parameters of anodic oxidation （such as voltage, the concentration of sulphuric acid, anodization time and current density） on the aperture and the crystalline phase of the TiO2 porous film were systematically investigated. The results indicate that the increase of current density facilitates the augment of the aperture and the generation of anatase and mille. In addition, the forming mechanism of anatase and mille TiO2 porous films was discussed.

Oxidation Kinetics of (111) Silicon Monocrystal and Morphology of Oxide Film in Dry Oxygen Atmosphere

1. Introduction Thermal oxidation of silicon monocrystalis a very important process in fabricationof metal--oxide--semiconductor (MOS) devices.In recent years it has received great atten-tion. Various proposals for oxidation modeshave been made by different groups.Now most of the authors working in thisfield hold the view that the oxidation rateof silicon obeys a typical parabolic rule,that is, the oxidation reaction is controlledby diffusion. The experimental data inRef. can be taken and a kinetic curve

P-Type Nitrogen-Doped ZnO Films Prepared by In-Situ Thermal Oxidation of Zn_3N_2 Films

P-type nitrogen-doped ZnO films are prepared successfully by in-situ thermal oxidation of Zn3N2 films. The prepared films are characterized by x-ray diffraction, non-Rutherford back.scattering （non-RBS） spectroscopy, x- ray photoelectron spectroscopy, and photoluminescence spectrum. The results show that the Zn3N1 films start to transform to ZnO at 400℃ and the total nitrogen content decreases with the increasing annealing temperature. The p-type fihns are achieved at 500℃ with a low resistivity of 6.33Ω.cm and a high hole concentration of ＋8.82 × 10^17 cm-3, as well as a low level of carbon contamination, indicating that the substitutional nitrogen （No） is an effective acceptor in the ZnO：N film. The photoluminescence spectra show clear UV emissions and also indicate the presence of oxygen vacancy （Vo） defects in the ZnO：N films. The p-type doping mechanism is briefly discussed.

Study on Physical Process of Surface Oxidation of Rare Earth-Transition Metal Amorphous Magneto-Optical Thin Films

By using surface effects(Auger electron spectroscopy,X-ray photoelectron spectroscopy,polar Kerr effect)and volume effects(magnetization,torque curve)the physical process of surface oxidation of rare earth-transition metal amorphous magneto-optical thin films was studied in this paper.The rare earth elements oxidize preferentially and rich at the film surface,and the transition metals deplete in oxidation layer.Fe_2O_3 in the surface oxidation layer contributes to the planar magnetization,and thereby the anomalous peak appears near 180° on the torque curves and the amplitude of the peaks is related to the depth of surface oxidation layers.The iron bonds to oxygen easier than the cobolt.RE-Co magneto-optieal thin films have good properties of resistance to oxidation and humidity.

Morphology and Structure of SiO_2 Film Using Thermal Oxidation Process on(111)Silicon Crystals in Dry Oxygen Atmosphere

By means of scanning electron microscope(SEM)and high voltage electron microscope(HVEM)we have observed and analysed morphology and micro-structure of silicon oxide film with different thickness formed on(111)silicon monocrystal under dry oxygen atmosphere at 1100℃.Compared with their oxidation kinetic curves consisted of three stages,we suggested a mechanism on forming silicon oxide film.According to electron and X-ray diffraction analyses the silicon oxide films consisted of silica with different crystal structure.We also have discussed a stacking fault and a dislocation formed in the Si-Sio_2 interface region simulaneously forming silicon oxide film.

Green Fabrication of Freestanding Piezoceramic Films for Energy Harvesting and Virus Detection

Most electronics such as sensors,actuators and energy harvesters need piezoceramic films to interconvert mechanical and electrical energy.Transferring the ceramic films from their growth substrates for assembling electronic devices commonly requires chemical or physical etching,which comes at the sacrifice of the substrate materials,film cracks,and environmental contamination.Here,we introduce a van der Waals stripping method to fabricate large-area and freestanding piezoceramic thin films in a simple,green,and cost-effective manner.The introduction of the quasi van der Waals epitaxial platinum layer enables the capillary force of water to drive the separation process of the film and substrate interface.The fabricated lead-free film,Ba_(0.85)Ca_(0.15)Zr_(0.1)Ti_(0.9)O_(3)(BCZT),shows a high piezoelectric coefficient d_(33)=209±10 pm V−1 and outstanding flexibility of maximum strain 2%.The freestanding feature enables a wide application scenario,including micro energy harvesting,and covid-19 spike protein detection.We further conduct a life cycle analysis and quantify the low energy consumption and low pollution of the water-based stripping film method.

Development of high-strength magnesium alloys with excellent ignition-proof performance based on the oxidation and ignition mechanisms: A review

High reactivity and ease of ignition are the major obstacles for the application of Mg alloys in aerospace.Thus,the ignition mechanisms of Mg alloys should be investigated systematically,which can guide the ignition-proof alloy design.This article concludes the factors influencing the ignition resistance of Mg alloys from oxide film and substrate microstructure,and also the mechanisms of alloying elements improving the ignition resistance.The low strength is another reason restricting the development of Mg alloys.Therefore,at the last section,Mg alloys with the combination of high strength and good ignition-proof performance are summarized,including Mg-Al-Ca based alloys,SEN(Mg-Al-Zn-Ca-Y)alloys as well as Mg-Y and Mg-Gd based alloys.Besides,the shortages and the future focus of theses alloys are also reviewed.The aim of this article is to promote the understanding of oxidation and ignition mechanisms of Mg alloys and to provide reference for the development of Mg alloys with high strength and excellent ignition-proof performance at the same time.

Oxidation of Fe-Cr-Ni Alloys in a Low Oxygen Partial Pressure Atmosphere to Mitigate Coke Formation

Anti-coking oxide films were prepared on a 25Cr35Ni and 35Cr45Ni alloy surface under the low oxygen partialpressure atmosphere of a H2-H2O mixture. The composition and phase structure of the oxide films were analyzed by energydispersive spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The anti-cokingperformance of a mini tube made of a HP40 (25Cr35Ni) alloy was evaluated on a bench scale pyrolysis and coking test unit.The results showed that the surface Fe and Ni content decreased after the oxidation of the two alloys in a low oxygen partialpressure atmosphere. The oxide films were mainly composed of MnCr_(2)O_(4) and Cr_(2)O_(3). The average mass of coke in the minitube with oxide film decreased by 87% relative to that of a tube without an oxide film when the cracking temperature was 900℃. The ethylene, propylene, and butadiene yields in the pyrolysis tests were almost the same for the mini tubes withand without an oxide film. The oxide film on the alloy surface effectively inhibited catalytic filamentous coke formation.An industrial test showed that the run length of the cracking furnace with the in-situ coating technology was significantlyextended.

Low-temperature ferromagnetism in tensile-strained LaCoO_(2.5)thin film

The origin of ferromagnetism in epitaxial strained LaCoO_(3-x)films has long been controversial.Here,we investigated the magnetic behavior of a series of oxygen vacancy-ordered LaCoO_(3-x)films on different substrates.Obvious ferromagnetism was observed in perovskite LaCoO_(3)/LSAT(LSAT=(LaAlO_(3))0.3(SrAlTaO_(6))_(0.7))and LaCoO_(3)/SrTiO_(3) films,while LaCoO_(3)/LaAlO_(3)films showed weak ferromagnetic behavior.Meanwhile,LaCoO_(2.67) films exhibited antiferromagnetic behavior.An unexpected low-temperature ferromagnetic phenomenon with a Curie temperature of~83 K and a saturation magnetization of~1.2μB/Co was discovered in 15 nm thick LaCoO_(2.5)/LSAT thin films,which is probably related to the change in the interface CoO_(6) octahedron rotation pattern.Meanwhile,the observed ferromagnetism gradually disappeared as the thickness of the film increased,indicating a relaxation of tensile strain.Analysis suggests that the rotation and rhombohedral distortion of the CoO_(6) octahedron weakened the crystal field splitting and promoted the generation of the ordered high-spin state of Co^(2+).Thus the super-exchange effect between Co^(2+)(high spin state),Co^(2+)(low spin state)and Co^(2+)(high spin state)produced a low-temperature ferromagnetic behavior.However,compressive-strained LaCoO_(2.5)film on a LaAlO_(3)substrate showed normal anti-ferromagnetic behavior.These results demonstrate that both oxygen vacancies and tensile strain are correlated with the emergent magnetic properties in epitaxial LaCoO_(3-x)films and provide a new perspective to regulate the magnetic properties of transition oxide thin films.

High-temperature oxidation behavior of a cast Ti-47.5Al-2.5V-1.0Cr-0.2Zr alloy

The oxidation behavior of the Ti-47.5Al-2.5V-1.0Cr-0.2Zr alloy at 900℃ was investigated at different oxidation times(5,20,60 and 100 h).The results show that the total weight gain of the alloy after 100 h at 900℃ oxidation is 9.1 g·m^(-2),and the oxidation rate decreases with oxidation time.The oxides on the alloy surface are mainly TiO_(2) and Al_(2)O_(3).At the beginning of oxidation(5 h),the oxide film is relatively complete,thin,and the interface between the oxide layer and the matrix is virtually flat.At the end of oxidation(100 h),the thickness of the oxide film is expanded,cracking and spalling occur,and the spalling form is intra-film spalling.At the same time,oxygen is mainly distributed in the oxide film and the oxygen content in the alloy substrate is reduced,confirming that the TiAl alloy has a certain oxidation stability at 900℃.From the outer surface of the oxide layer to the matrix,the TiO_(2) content increases and the Al_(2)O_(3) content decreases.Oxidation proceeds to completion in this system via the dissolution and diffusion of O atom.

Wear-resisting Oxide Films for 900℃

A study was conducted to develop low-friction, wear-resistant surfaces on high temperature alloys for the temperature range from 26℃ to 900℃. The approach investigated consists of modifying the naturally occurring oxide film in order to improve its tribological properties. Improvement is needed at low temperatures where the oxide film, previously formed at high temperature, spalls due to stresses induced by sliding. Experiments with Ti, W and Ta additions show a beneficial effect when added to Ni and Ni-base alloys. Low friction can be maintained down to 100℃ from 900℃. For unalloyed Ni friction and surface damage increases at 400℃ to 500℃. Two new alloys were perpared based on the beneficial results of binary alloys and ZrO2 diffusion in Ni.Low friction at temperature above 500℃ and reasonable values (0.32~0.42) at low temperature are obtained.

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.

STOCHASTIC CRACKING AND HEALING BEHAVIORS OF THIN FILMS DURING REACTION-DIFFUSION GROWTH

The stochastic cracking and healing behaviors of reaction-diffusion growth of thin filmswere studied by means of Markov processes analysis. We chose the thermal growth ofoxide scales on metals as an example of reaction-diffusion growth. The thermal growthof oxide films follows power law when no cracking occurs. Our results showed that thegrowth kinetics under stochastic cracking and healing conditions was different fromthat without cracking. It might be altered to either pseudo-linear or pseudo-power lawsdependent upon the intensity and frequency of the cracking of the films. When thehoping items dominated, the growth followed pseudo-linear law; when the diffusionalitems dominated, it followed pseudo-power law with the exponentials lower than theintrinsical values. The numerical results were in good agreement with the meassuredkinetics of isothermal and cyclic oxidation of NiAl-0.1 Y (at. %) alloys in air at 1273K.

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.

Micro-analysis of high-temperature oxidation-resistance of a new kind of heat-resistant grid plate in grate-kiln

To further improve the oxidation-resistance of materials and reduce the cost of grid plates in grate-kiln, a new kind of heat-resistant grid plate was developed. The microstructure of this grid plate with a life more than 18 months was studied by XRD, SEM and EDS techniques. The results show that high hardness, high intensity and good impact property make the new kind of heat-resistant grid plate and its oxide film have a higher resistance to deformation and abrasion at 900-1000℃ Besides, small grain size is beneficial to form a complete protective oxide film. The oxide film composed of SiO2 layer, Cr2O3 layer and Fe2O3 layer is rather thin and bonds closely with the backing. The forming of the chemical stable nickel-rich layer increases the density of Cr2O3 layer.