Comparative investigation of microstructure and high-temperature oxidation resistance of high-velocity oxy-fuel sprayed CoNiCrAlY/nano-Al_(2)O_(3) composite coatings using satellited powders

Satellited CoNiCrAlY–Al_(2)O_(3)feedstocks with 2wt%, 4wt%, and 6wt% oxide nanoparticles and pure CoNiCrAlY powder were deposited by the high-velocity oxy fuel process on an Inconel738 superalloy substrate. The oxidation test was performed at 1050℃ for 5, 50, 100,150, 200, and 400 h. The microstructure and phase composition of powders and coatings were characterized by scanning electron microscopy and X-ray diffraction, respectively. The bonding strength of the coatings was also evaluated. The results proved that with the increase in the percentage of nanoparticles(from 2wt% to 6wt%), the amount of porosity(from 1vol% to 4.7vol%), unmelted particles, and roughness of the coatings(from 4.8 to 8.8 μm) increased, and the bonding strength decreased from 71 to 48 MPa. The thicknesses of the thermally grown oxide layer of pure and composite coatings(2wt%, 4wt%, and 6wt%) after 400 h oxidation were measured as 6.5, 5.5, 7.6, and 8.1 μm, respectively.The CoNiCrAlY–2wt% Al_(2)O_(3)coating showed the highest oxidation resistance due to the diffusion barrier effect of well-dispersed nanoparticles. The CoNiCrAlY–6wt% Al_(2)O_(3)coating had the lowest oxidation resistance due to its rough surface morphology and porous microstructure.

Effect of La_2O_3/Ce O_2 particle size on high-temperature oxidation resistance of electrodeposited Ni-La_2O_3/Ce O_2 composites

Ni-La2O3/CeO2 composite films were prepared by electrodeposition from a nickel sulfate bath containing certain content of micrometer and nanometer La2O3/CeO2 particles. The effect of La2O3 or CeO2 particle size on the oxidation resistance of the electrodeposited Ni-La2O3/CeO2 composites in air at 1000 °C was studied. The results indicate that, compared with the electrodeposited Ni-film, Ni-La2O3/CeO2 composites exhibit a superior oxidation resistance due to the codeposited La2O3 or CeO2 particles blocking the outward diffusion of nickel. Moreover, compared with nanoparticles, La2O3 or CeO2 microparticles have stronger effect because La2O3 or CeO2 microparticles also act as a diffusion barrier layer at the onset of oxidation.

Effect of Ti and Ta content on the oxidation resistance of Co-Ni-based superalloys

Co-Ni-based superalloys are known for their capability to function at elevated temperatures and superior hot corrosion and thermal fatigue resistance.Therefore,these alloys show potential as crucial high-temperature structural materials for aeroengine and gas turbine hot-end components.Our previous work elucidated the influence of Ti and Ta on the high-temperature mechanical properties of alloys.However,the intricate interaction among elements considerably affects the oxidation resistance of alloys.In this paper,Co-35Ni-10Al-2W-5Cr-2Mo-1Nb-xTi-(5−x)Ta alloys(x=1,2,3,4)with varying Ti and Ta contents were designed and compounded,and their oxidation resistance was investigated at the temperature range from 800 to 1000℃.After oxidation at three test conditions,namely,800℃for 200 h,900℃for 200 h,and 1000℃for 50 h,the main structure of the oxide layer of the alloy consisted of spinel,Cr_(2)O_(3),and Al_(2)O_(3)from outside to inside.Oxides consisting of Ta,W,and Mo formed below the Cr_(2)O_(3)layer.The interaction of Ti and Ta imparted the highest oxidation resistance to 3Ti2Ta alloy.Conversely,an excessive amount of Ti or Ta resulted in an adverse effect on the oxidation resistance of the alloys.This study reports the volatilization of W and Mo oxides during the oxidation process of Co-Ni-based cast superalloys with a high Al content for the first time and explains the formation mechanism of holes in the oxide layer.The results provide a basis for gaining insights into the effects of the interaction of alloying elements on the oxidation resistance of the alloys they form.

Oxidation behavior and improvement in nonflammability of LPSO-type Mg–Zn–Y–Sr alloy

Mg_(97)Zn_(1)Y_(2)alloys with high ignition temperatures were developed by adding Sr.The addition of Sr resulted in the formation of a uniform and thin Y_(2)O_(3)film.Mg–Zn–Y alloys containing at least 0.25 at.%Sr exhibited ignition temperatures of 1270–1320 K.As a result of EDS measurement,Sr was found to be concentrated in the Y_(2)O_(3)film.In addition,a mixed film of MgO and Sr O formed on the outer layer in the 1.5 at.%Sr-containing Mg_(97)Zn_(1)Y_(2)alloy.These findings suggest that the uniform and thin Y_(2)O_(3)film that maintains high soundness at high temperatures was formed owing to valence control and the formation of a protective outer oxide film.

Acetic acid-assisted mild dealloying of fine CuPd nanoalloys achieving compressive strain toward high-efficiency oxygen reduction and ethanol oxidation electrocatalysis

Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Herein,to address the deficiencies associated with the commonly used dealloying methods,for example,electrochemical and sulfuric acid/nitric acid treatment,we report an acetic acid-assisted mild strategy to dealloy Cu atoms from the outer surface layers of CuPd alloy nanoparticles to achieve high-efficiency electrocatalysis for oxygen reduction and ethanol oxidation in an alkaline electrolyte.The leaching of Cu atoms by acetic acid exerts an additional compressive strain effect on the surface layers and exposes more active Pd atoms,which is beneficial for boosting the catalytic performance of a dealloyed catalyst for the oxygen reduction reaction(ORR)and the ethanol oxidation reaction(EOR).In particular,for ORR,the CuPd nanoparticles with a Pd/Cu molar ratio of 2:1 after acetic dealloying show a half-wave potential of 0.912 V(vs.RHE)and a mass activity of 0.213 AmgPd^(-1) at 0.9 V,respectively,while for EOR,the same dealloyed sample has a mass activity and a specific activity of 8.4 Amg^(-1) and 8.23 mA cm^(-2),respectively,much better than their dealloyed counterparts at other temperatures and commercial Pd/C as well as a Pt/C catalyst.

High-temperature stress suppresses allene oxide cyclase 2 and causes male sterility in cotton by disrupting jasmonic acid signaling

Cotton(Gossypium spp.) yield is reduced by stress. In this study, high temperature(HT) suppressed the expression of the jasmonic acid(JA) biosynthesis gene allene oxide cyclase 2(GhAOC2), reducing JA content and causing male sterility in the cotton HT-sensitive line H05. Anther sterility was reversed by exogenous application of methyl jasmonate(MeJA) to early buds. To elucidate the role of GhAOC2 in JA biosynthesis and identify its putative contribution to the anther response to HT, we created gene knockout cotton plants using the CRISPR/Cas9 system. Ghaoc2 mutant lines showed male-sterile flowers with reduced JA content in the anthers at the tetrad stage(TS), tapetum degradation stage(TDS), and anther dehiscence stage(ADS). Exogenous application of MeJA to early mutant buds(containing TS or TDS anthers) rescued the sterile pollen and indehiscent anther phenotypes, while ROS signals were reduced in ADS anthers. We propose that HT downregulates the expression of GhAOC2 in anthers, reducing JA biosynthesis and causing excessive ROS accumulation in anthers, leading to male sterility. These findings suggest exogenous JA application as a strategy for increasing male fertility in cotton under HT.

Synthesis of phosphonated graphene oxide by electrochemical exfoliation to enhance the performance and durability of high-temperature proton exchange membrane fuel cells

The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PGO)with a P/O ratio of 8.5%was quickly synthesised by one-step electrochemical exfoliation based on a three-dimensiaonal(3D)printed reactor and natural graphite flakes.Compared with the GO prepared by the two-step electrochemical exfoliation method,the PGO synthesized by the one-step electrochemical exfoliation can better improve the performance of the membrane-electrode-assembly(MEA)based on the polybenzimidazole(PBI)membrane in the HTPEMFC.The doping of 1.5 wt%GO synthesised by electrochemical exfoliation with the 2-step method or reactor method in PBI increased the peak power density by 17.4%or 35.4%compared to MEA based on pure PBI membrane at 150℃,respectively.In addition,the doping of PGO in PBI improves its durability under accelerated stress test(AST).

Gas-phase oxidation of NO at high pressure relevant to sour gas compression purification process for oxy-fuel combustion flue gas

The removal of NO from oxy-fuel combustion is typically incorporated in sour gas compression purification process. This process involves the oxidation of NO to NO2 at a high pressure of 1–3 MPa, followed by absorption of NO2 by water. In this pressure range, the NO conversion rates calculated using the existing kinetic constants are often higher than those obtained experimentally. This study aimed to achieve the regression of kinetic parameters of NO oxidation based on the existing experimental results and theoretical models.Based on three existing NO oxidation mechanisms, first, the expressions for NO conversion against residence time were derived. By minimizing the mean-square errors of NO conversion ratio, the optimum kinetic rate constants were obtained. Without considering the reverse reaction for NO oxidation, similar mean-square errors for NO conversion ratio were calculated. Considering the reverse reaction for NO oxidation based on the termolecular reaction mechanism, the minimum mean-square error for NO conversion ratio was obtained. Thus, the optimum NO oxidation rate in the pressure range 0.1–3 MPa can be expressed as follows:-d[NO]/dt=d[NO2]/dt=0.0026[NO]2[O2]-0.0034[NO2]2 Detailed elementary reactions for N2/NO/NO2/O2 system were established to simulate the NO oxidation rate. A sensitivity analysis showed that the critical elementary reaction is 2 NO + O2? 2 NO2. However, the simulated NO conversions at a high pressure of 10–30 bar are still higher than the experimental values and similar to those obtained from the models without considering the reverse reaction for NO oxidation.

Influencing factors and mechanism of high-temperature oxidation of high-entropy alloys: A review

High-temperature oxidation is a common failure in high-temperature environments,which widely occur in aircraft engines and aerospace thrusters;as a result,the development of anti-high-temperature oxidation materials has been pursued.Ni-based alloys are a common high-temperature material;however,they are too expensive.High-entropy alloys are alternatives for the anti-oxidation property at high temperatures because of their special structure and properties.The recent achievements of high-temperature oxidation are reviewed in this paper.The high-temperature oxidation environment,temperature,phase structure,alloy elements,and preparation methods of high-entropy alloys are summarized.The reason why high-entropy alloys have anti-oxidation ability at high temperatures is illuminated.Current research,material selection,and application prospects of high-temperature oxidation are introduced.

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.

High-temperature oxidation behavior of 9Cr‒5Si‒3Al ferritic heat-resistant steel

To improve the oxidation properties of ferritic heat-resistant steels,an Al-bearing 9Cr‒5Si‒3Al ferritic heat-resistant steel was designed.We then conducted cyclic oxidation tests to investigate the high-temperature oxidation behavior of 9Cr‒5Si and 9Cr‒5Si‒3Al ferritic heat-resistant steels at 900 and 1000℃.The characteristics of the oxide layer were analyzed by X-ray diffraction,scanning electron microscopy,and energy dispersive spectroscopy.The results show that the oxidation kinetics curves of the two tested steels follow the parabolic law,with the parabolic rate constant kp of 9Cr‒5Si‒3Al steel being much lower than that of 9Cr‒5Si steel at both 900 and 1000℃.The oxide film on the surface of the 9Cr‒5Si alloy exhibits Cr2MnO4 and Cr2O3 phases in the outer layer after oxidation at 900 and 1000℃.However,at oxidation temperatures of 900 and 1000℃,the oxide film of the 9Cr‒5Si‒3Al alloy consists only of Al2O3 and its oxide layer is thinner than that of the 9Cr‒5Si alloy.These results indicate that the addition of Al to the 9Cr‒5Si steel can improve its high-temperature oxidation resistance,which can be attributed to the formation of a continuous and compact Al2O3 film on the surface of the steel.

Analysis on high-temperature oxidation and growth stress of iron-based alloy using phase field method

High-temperature oxidation is an important property to evaluate thermal protection materials. However, since oxidation is a complex process involving microstructure evolution, its quantitative analysis has always been a challenge. In this work, a phase field method （PFM） based on the thermodynamics theory is developed to simulate the oxidation behavior and oxidation induced growth stress. It involves microstructure evolution and solves the problem of quantitatively computational analysis for the oxidation behavior and growth stress. Employing this method, the diffusion process, oxidation performance, and stress evolution axe predicted for Fe-Cr-A1-Y alloys. The numerical results agree well with the experimental data. The linear relationship between the maximum growth stress and the environment oxygen concentration is found. PFM provides a powerful tool to investigate high-temperature oxidation in complex environments.

High-temperature oxidation behavior of heat resistant stainless steel 1.4828

The kinetic curves of the high-temperature oxidation of austenitic heat resistant stainless steel 1. 4828 at 1 050 ℃ were measured using a weighing method. It is shown that the oxidation curves at 1 050 ℃ followed the parabolic line law, and after 250 h of oxidation, the mass gain was about 80 g/m2. The surface morphology and structure of the oxide layers were studied by scanning electron microscopy and X-ray diffraction. A complicated oxide layer obtained at 1 050 ℃ was mainly composed, from inner to outer, of （FeSi） 3 04, Cr2 03, Fe2 03, and spinel oxides FeCr204 and NiMn204.

High-temperature oxidation behavior of austenitic stainless steel Cr20Ni12Si2RE

Austenitic stainless steel Cr20 Ni12 Si2 RE was developed for use in hot-end components of automobile exhaust systems,especially in automobiles designed according to the China VI emission standard. The hightemperature oxidation kinetic curve of Cr20 Ni12 Si2 RE at 1 050 ℃ was obtained using the weighting method. The oxidation curves exhibit the parabolic law at 1 050 ℃; after 250 h of oxidation,the mass gain was 22 g/m^2. The morphology,structure,and composition of the oxide film were examined using scanning electron microscopy and Xray diffraction methods. A thin,stable,and dense spinel oxide film obtained after 250 h of oxidation at 1 050 ℃ was mainly composed of( Mn_(0.87)Fe_(0.13))( Mn_(0.13)Fe_(0.87)Cr) O_4 and Cr_2 O_3 with a silicon-containing oxide underneath. The addition of rare earth elements was found to restrict further diffusion of metallic atoms from the austenite toward the oxide film,and consequently,led to a low growth rate of the oxide film. The inner silicon-containing oxide was produced by the diffusion of oxygen atoms and enhanced the coherent strength of the oxide film.

Effect of warm acupuncture on nitric oxide synthase and calcitonin gene-related peptide in a rat model of lumbar nerve root compression

BACKGROUND： Varying degrees of inflammatory responses occur during lumbar nerve root compression. Studies have shown that nitric oxide synthase （NOS） and calcitonin gene-related peptide （CGRP） are involved in secondary disc inflammation. OBJECTIVE： To observe the effects of warm acupuncture on the ultrastructure of inflammatory mediators in a rat model of lumbar nerve root compression, including NOS and CGRP contents. DESIGN, TIME AND SETTING： Randomized, controlled study, with molecular biological analysis, was performed at the Experimental Center, Sixth People＇s Hospital Affiliated to Shanghai Jiao Tong University, between September 2006 and April 2007. MATERIALS： Acupuncture needles and refined Moxa grains were purchased from Shanghai Taicheng Technology Development Co., Ltd., China; Mobic tablets were purchased from Shanghai Boehringer Ingelheim Pharmaceuticals Co., Ltd., China; enzyme linked immunosorbent assay （ELISA） kits for NOS and CGRP were purchased from ADL Biotechnology, Inc., USA. METHODS： A total of 50, healthy, adult Sprague-Dawley rats, were randomly divided into five groups normal, model, warm acupuncture, acupuncture, and drug, with 10 rats in each group. Rats in the four groups, excluding the normal group, were used to establish models of lumbar nerve root compression. After 3 days, Jiaji points were set using reinforcing-reducing manipulation in the warm acupuncture group. Moxa grains were burned on each needle, with 2 grains each daily. The acupuncture group was the same as the warm acupuncture group, with the exception of non-moxibustion. Mobic suspension （3.75 mg/kg） was used in the oral drug group, once a day. Treatment of each group lasted for 14 consecutive days. Modeling and medication were not performed in the normal group. MAIN OUTCOME MEASURES： The ultrastructure of damaged nerve roots was observed with transmission electron microscopy; NOS and CGRP contents were measured using ELISA. RESULTS： The changes of the radicular ultramicrostructure were characterized by Wallerian degeneration; nerve fibers were clearly demyelinated; axons collapsed or degenerated; outer Schwann cell cytoplasm was swollen and its nucleus was compacted. Compared with the normal group, NOS and CGRP contents in the nerve root compression zone in the model group were significantly increased （P 〈 0.01）. Nerve root edema was improved in the drug, acupuncture and the warm acupuncture groups over the model group. NOS and CGRP expressions were also decreased with the warm acupuncture group having the lowest concentration （P 〈 0.01）. CONCLUSION： In comparison to the known effects of Mobic drug and acupuncture treatments, the warm acupuncture significantly decreased NOS and CGRP expression which helped improve the ultrastructure of the compressed nerve root.

Enhanced high-temperature performance of Li-rich layered oxide via surface heterophase coating

Li-rich layered oxides have become one of the most concerned cathode materials for high-energy lithiumion batteries, but they still suffer from poor cycling stability and detrimental voltage decay, especially at elevated temperature. Herein, we proposed a surface heterophase coating engineering based on amorphous/crystalline Li3 PO4 to address these issues for Li-rich layered oxides via a facile wet chemical method. The heterophase coating layer combines the advantages of physical barrier effect achieved by amorphous Li3 PO4 with facilitated Li+diffusion stemmed from crystalline Li3 PO4. Consequently, the modified Li(1.2) Ni(0.2) Mn(0.6) O2 delivers higher initial coulombic efficiency of 92% with enhanced cycling stability at 55 °C(192.9 mAh/g after 100 cycles at 1 C). More importantly, the intrinsic voltage decay has been inhibited as well, i.e. the average potential drop per cycle decreases from 5.96 mV to 2.99 mV. This surface heterophase coating engineering provides an effective strategy to enhance the high-temperature electrochemical performances of Li-rich layered oxides and guides the direction of surface modification strategies for cathode materials in the future.

A comparison between high temperature catalytic and persulfate oxidation for the determination of total dissolved nitrogen in natural waters

Total dissolved nitrogen(TDN) is an important parameter for assessing the nutrient cycling and status of natural waters.The accurate determination of TDN in natural waters is essential for assessing its contents and distinguishing different forms of nitrogen in the water.The TDN in various systems has been largely documented,and the concentrations of TDN are usually obtained using high-temperature catalytic(HTC) or persulfate oxidation(PO).However,the accuracy of these methods and their suitability for all types of natural waters are still unclear.To explore both methods in-depth,assorted samples were tested,including eight solutions composed of nitrogen-containing compounds(3 dissolved inorganic nitrogen fractions:NO_(3)^(-),NO_(2)^(-)and NH_(4)^(+);5 organic compounds:EDTA-2Na,vitamin B1,vitamin B12,amino acids,and urea) and 105 natural waters which were collected from an open ocean(Northwest Pacific Ocean,28),a marginal sea(Yellow Sea,34),an estuary(Huanghe River mouth,31),rivers(Huanghe River,4;Licun River,4),and precipitations(4 samples).The results showed that heterocycles and molecular dimensions had certain effects on the oxidation efficiency of the PO method but had little effect on HTC.There was no significant difference between the two methods for natural waters,but HTC was more suitable for deep-sea samples with low TDN concentrations(less than 10 μmol/L) and low organic activity.Overall,HTC has a relatively simple measurement process,a high degree of automation,and low error.Therefore,HTC can be recommended to determine the TDN of samples in freshwater and seawater.

Effect of inner oxidant on self-propagating high-temperature synthesis of MnZn-ferrite powder

Using KClO3 as an inner oxidant, MnZn-ferrite powder was synthesized by a self-propagating high-temperature synthesis (SHS) process in normal air atmosphere. The effects of the inner oxidant on combustion temperature, combustion velocity, microstructure and the phase of the product were investigated by XRD and SEM,respectively. The results show that a highly ferritized powder can be obtained as well as the highest combustion temperature and the highest combustion velocity when the inner oxidant content m equals 54(k-16).

Corrosion evolution of high-temperature formed oxide film on pure Sn solder substrate

The evolution of morphology, composition, thickness and corrosion resistance of the oxide film on pure Sn solder substrate submitted to high-temperature aging in 150 °C dry atmosphere was investigated. The results indicate that high-temperature aging accelerates the dehydration of Sn(OH)_(4)in the pre-existing native oxide film to form SnO_(2)and facilitates the oxidation of fresh Sn substrate, resulting in the gradual increase in oxide film thickness and surface roughness with prolonging aging time. However, the corrosion resistance of the film initially is enhanced and then deteriorated with an extending aging time. Besides, the formation and evolution mechanisms of the oxide film with aging time were discussed.

High-temperature elemental segregation induced structure degradation in high-entropy fluorite oxide

Fluorite-structured oxides constitute an important category of oxides with a wide range of high-temperature applications.Following the concept of high entropy,high-entropy fluorite oxides(HEFOs)have showcased intriguing high-temperature application potential.However,unlocking this potential necessitates an assessment of their long-term stability under high-temperature conditions.In this study,we conducted a prolonged heat treatment at 1000℃on typical HEFO,specifically(CeHfZrGdLa)O_(x).After 100 h,high-intensity X-ray diffraction(XRD)revealed a transition from a single-phase fluorite to a multi-phase configuration.Further investigation by analytical electron microscoy(AEM)demonstrated that this degradation resulted from facilitated element diffusion and consequent escalating chemical fluctuation at high temperatures,leading to spontaneous segregation and separation of Ce and La elements,forming Ce-rich,La-poor,and La-rich phases.Notably,the La-rich phase spontaneously transformed from a fluorite structure(space group Fm3m)to a bixbyite structure(space group Ia3)at elevated temperatures,resulting in the appearance of superstructure reflection in XRD profiles and electron diffraction patterns.Despite the intricate phase decomposition,the energy band gap showed minimal variation,suggesting potential property stability of(CeHfZrGdLa)O_(x)across a broad range of compositions.These findings offer valuable insights into the future applications of HEFOs.