Growth kinetics and mechanism of microarc oxidation coating on Ti-6Al-4V alloy in phosphate/silicate electrolyte

Microarc oxidation(MAO)is an effective surface treatment method for Ti alloys to allow their application in extreme environments.Here,binary electrolytes consisting of different amounts of sodium phosphate and sodium silicate were designed for MAO.The surface morphology,composition,and properties of MAO coatings on Ti-6Al-4V alloy treated in 0.10 mol/L electrolyte were investigated to reveal the effect of PO_(4)^(3-)and SiO_(3)^(2-)ray diffraction,and potentiodynamic polarization.The results showed that PO_(4)^(3-)is beneficial for generating microarcs and forming pores within the coating,resulting in a thick but porous coating.SiO_(3)^(2-)eration of microarcs,resulting in a thin dense coating.The thickness,density,phases content,and polarization resistance of the MAO coatings are primarily affected by the intensity of microarcs for low SiO_(3)^(2-)ciently high.The thickness of MAO coatings obtained in P/Si electrolytes shows a piecewise linear increase with increasing process time during the three stages of microarc discharge.SiO_(3)^(2-)discharge,but slows down the growth of the coating formed in the next stage.

Carbon dots regulate the interface electron transfer and catalytic kinetics of Pt-based alloys catalyst for highly efficient hydrogen oxidation

The regulation of interface electron-transfer and catalytic kinetics is very important to design the efficient electrocatalyst for alkaline hydrogen oxidation reaction(HOR).Here,we show the Pt-Ni alloy nanoparticles(PtNi_(2))have an enhanced HOR activity compared with single component Pt catalyst.While,the interface electron-transfer kinetics of PtNi_(2)catalyst exhibits a very wide electron-transfer speed distribution.When combined with carbon dots(CDs),the interface charge transfer of PtNi_(2)-CDs composite is optimized,and then the PtNi_(2)-5 mg CDs exhibits about 2.67 times and 4.04 times higher mass and specific activity in 0.1 M KOH than that of 20%commercial Pt/C.In this system,CDs also contribute to trapping H^(+)and H_(2)O generated during HOR,tuning hydrogen binding energy(HBE),and regulating interface electron transfer.This work provides a deep understanding of the interface catalytic kinetics of Pt-based alloys towards highly efficient HOR catalysts design.

Steady-state kinetics and osillation phenomena for complete oxidation of benzene over Pt/Al_2O_3 catalyst

The steady-state kinetics for complete oxidation of benzene over has been investigated by the external recycling reactor. The kinetics equation was described by the L-H model of adsorption of benzene and oxygen with the inhibition of carbon dioxide. The parameters of the kinetics model were estimated by the method of orthogonal design. The heats of adsorption of benzene, oxygen and carbon dioxide were determined by the method of gas-adsorption chromatography. The details of oscillations of complete oxidation of benzene were investigated.

Selective oxidation of ethylbenzene catalyzed by fluorinated metalloporphyrins with molecular oxygen

This paper reported the oxidation of ethylbenzene catalyzed by fluorinated metalloporphyrins under mild conditions without any additives. The results showed that the cobalt(II)(5,10,15,20-tetrakis(pentafluorophenyl))porphyrin was the best catalyst among the fluorinated metalloporphyrins. The conversion of ethylbenzene reached 38.6%, the selectivity to acetophenone reached 94.0%, and the turnover number is 2719 under the optimal conditions.

Decomposition kinetics of dimethyl methylphospate(chemical agent simulant) by supercritical water oxidation

Supercritical water oxidation （SCWO） has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An important design consideration in the development of supercritical water oxidation is the information of decomposition rate. In this paper, the decomposition rate of dimethyl methylphosphonate（DMMP）, which is similar to the nerve agent VX and GB（Sarin） in its structure, was investigated under SCWO conditions. The experiments were performed in an isothermal tubular reactor with a H2O2 as an oxidant. The reaction temperatures were ranged from 398 to 633℃ at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon （TOC） on the liquid effluent samples. It is found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 s at 555℃. On the basis of data derived from experiments, a global kinetic equation for the decomposition of DMMP was developed. The model predictions agreed well with the experimental data.

Effect of REs(Y,Nd)addition on high temperature oxidation kinetics,oxide layer characteristic and activation energy of AZ80 alloy

The oxidation behaviors of AZ80,AZ8O-0.32 Y and AZ8O-0.38 Nd(wt.%)alloys were researched at 413℃,420℃,427v and 433℃for up to 6 h in air environment via a high precision analytical balance,a laser confocal microscope,differential scanning calorimeter(DSC)analysis,X-ray diffraction(XRD)analysis,scanning electron microscope(SEM)observation,and X-ray photoelectron spectroscopy(XPS)analysis.The results show that the weight gain and oxidation rate of AZ80 are reduced significantly,the initiation form and propagation of cracks in oxide layer are changed.Compact and protective oxide layer forms on alloy surface with Y or Nd addition.And the activation energies of AZ80,AZ80-0.32Y and AZ8O-0.38Nd alloys calculated via Arrhenius equation are 82.556 kJ/mol,177.148kJ/mol and 136.738 kJ/mol,respectively.

Isothermal Oxidation Kinetics of Artificial Magnetite Pellets

In order to establish the kinetics of oxidation of artificial magnetite pellets, we comprehensively studied kinetics of the oxidation of artificial magnetite pellets from low temperature to high temperature using chemical analysis. The results show that when the oxidation temperature is below 1 073 K（800 ℃）, the reaction is controlled by the step of internal diffusion, and the model function is 23 G（a） =1-3（1-x）;+2（1-x）(α, reaction degree). When the temperature is above 1 073 K（800 ℃）, the reaction mechanism was chemical reaction, and the model function is 13 G（a） =1-（1-x）;. The apparent activation energy for the oxidation of artificial magnetite pellets was also determined, which was 8.90 kJ/mol for the low temperature and 67.79 kJ/mol for the high temperature. Based on the derived kinetic equation for the oxidation of artificial magnetite pellets, the calculated value is consistent with the experimental data. Compared with that of nature magnetite pellets, the apparent activation energy is decreased obviously, which indicates that the artificial magnetite pellets are oxidized more easily than nature magnetite pellets.

Competitive oxidation behavior of Ni-based superalloy GH4738 at extreme temperature

A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isothermal experiments. As a result of the competitive diffusion of alloying elements, the oxide scale included an outermost porous oxide layer (OOL), an inner relatively dense oxide layer (IOL), and an internal oxide zone (IOZ), depending on the temperature and time. A high temperature led to the formation of large voids at the IOL/IOZ interface. At 1200℃, the continuity of the Cr-rich oxide layer in the IOL was destroyed, and thus, spallation occurred. Extension of oxidation time contributed to the size of Al-rich oxide particles with the increase in the IOZ. Based on this finding,the oxidation kinetics of GH4738 was discussed, and the corresponding oxidation behavior at 900-1100℃ was predicted.

Effects of chlorine content and position of chlorinated phenols on their oxidation kinetics by potassium permanganate

Chlorine content and position of chlorinated phenols have many significant effects on the reactivity of oxido-reduction. The effects of chlorine content and position of chlorinated phenols on their oxidation kinetics by potassium permanganate were evaluated through different kinetics studies. Since chlorine was an electron withdrawing atom, the substitution of chlorine on the aromatic ring decreased the oxidation rate constant by σ-electron withdrawing conductive effect. The substitution of chlorine at ortho or para position on the aromatic ring increased the oxidation rate constant by π-electron donating conjugative effect, and the conjugative effect could counteract the negative impact of the conductive effect to some extent. On the other hand, the substitution of chlorine at ortho position on the aromatic ring decreased the oxidation rate constant by steric hindrance effect. The oxidation rate constants of phenol and chlorinated phenols studied decreased as follow order: 4-chlorophenol>2,4-dichlorophenol>phenol>2,6-dichlorophenol.

Effect of inhibitors on macroscopical oxidation kinetics of calcium sulfite

In the presence of inhibitors, the macroscopical oxidation kinetics of calcium sulfite, the main byproduct in wet limestone scrubbing, was studied for the first time by adding different inhibitors and varying pH, concentration of calcium sulfite, oxygen partial pressure, concentration of inhibitors and temperature. The mathematical model about the general oxidation reaction was established, which was controlled by three steps involving dissolution of calcium sulfite, mass transfer of oxygen and chemical reaction in the solution. It was concluded that the general reaction was controlled by mass transfer of oxygen under uncatalyzed conditions, while it was controlled by dissolution of calcium sulfite after adding three kinds of inhibitors. Thus, the theory was provided for investigating the mechanism and oxidation kinetics of sulfite. The beneficial references were also supplied for design of oxidation technics in the wet limestone scrubbing.

Study on Influencing Factors and Kinetics of Removal of Ammonia Nitrogen from High Salinity Wastewater by Sodium Hypochlorite Oxidation

The influencing factors and kinetics of oxidative degradation of ammonia nitrogen in high salinity wastewater by sodium hypochlorite oxidation( Na Cl O) were studied. The results showed that the degradation process of ammonia nitrogen by sodium hypochlorite accorded with a pseudo first-order kinetics model,and the influencing factors included Na Cl O dosage,initial concentration of ammonia nitrogen,salinity,temperature,and so on. When Na Cl O dosage was 0. 6%( MCl∶ MN= 13. 76),the reaction rate constant was up to 0. 015 75 min^(-1). The higher the initial concentration of ammonia nitrogen was,the worse the effect of oxidation reaction was. When the initial concentration did not exceed 45 mg/L,the effect on oxidation reaction rate constant increased with the increase of the initial concentration. Low salinity had no effect on ammonia nitrogen oxidation.When salinity was higher than 2. 0%,the inhibition effect on ammonia nitrogen oxidation would increase,and the reaction rate constant decreased obviously with the increase of salinity. The improvement of reaction temperature was beneficial to ammonia oxidation degradation. As temperature increased from 10 to 35 ℃,the reaction rate constant rose from 0. 00188 to 0. 01043 min^(-1).

Experimental study on the oxidation kinetics of coal in typical coal mining areas of the Southern Junggar coalfield,Xinjiang,China

Coal spontaneous combustion(CSC)is a disaster associated with coal mining that leads to loss of coal resources and envi-ronmental and human health issues.To investigate kinetic characteristics for oxidation of coal,three coal samples were collected from different coal mining areas in the Southern Junggar coalfield.Subsequently,the collected coal samples were ground into different particle sizes and tested using microscopic and macroscopic methods,including thermal gravimetric analysis,Fourier transform infrared spectroscopy,X-ray diffraction,and temperature-programmed oxidation.The results obtained are as follows:the sharpest absorption peak(002)indicates that graphitization is high.Furthermore,the results show that the SKS coal sample is prone to spontaneous combustion;the greater the aromatic hydrocarbon content is,the more difficult it is for CSC to occur,while the opposite is true for oxygen-containing functional groups.The SKS data confirmed this conclusion;the rate for generation of CO and CO_(2)controlled the possibility of SKS oxidation at 110℃and provided an indication of the temperature.During the dehydration stage,the WD sample had the lowest activation energy,indicating that it was most susceptible to spontaneous combustion.During the combustion stage,the lowest activation energy was found for the SKS sample with particle sizes<0.075 mm,indicating that particle size was one of the factors affecting spontane-ous combustion.The activation energy for dehydration was significantly lower than that for combustion,which showed that the coal oxygen reaction was more likely to occur in the dehydration stage.Based on DSC curves,the SKS sample had the largest exothermicity,indicating that it would ignite more readily.

Selective aerobic oxidation of p-cresol with co-catalysts between metalloporphyrins and metal salts

A green and efficient method for the selective aerobic oxidation of p-cresol to p-hydroxybenzaldehyde catalyzed by co-catalysts between metalloporphyrins and metal salts was investigated and developed. The relationship between the synergistic catalytic effects and the composition as well as amount of co-catalysts was investigated. Moreover, the influence of different reaction conditions was studied in details. A high p-cresol conversion(N 99%) and p-hydroxybenzaldehyde selectivity(83%) were obtained using only 1.125 × 10^(-5) mol T(p-CH_3 O)PPFe^(III)Cl-Co(OAc)_2 used under mild, optimized reaction conditions. A possible mechanism for the reaction was also proposed. This work would be meaningful and instructive for the further researches and applications of co-catalyst system on oxidation of cresols and could give some enlightenment on the selectively catalytic oxidation of the side-chain alkyls of aromatics.

Immobilization of metalloporphyrins on CeO_2@SiO_2 with a core-shell structure prepared via microemulsion method for catalytic oxidation of ethylbenzene

Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.

Photocatalytic Oxidation Kinetics of Thiophene with Nano-F^-/Fe^(3+)/TiO_2

Photocatalytic oxidation kinetics of thiophene in n-octane/water extraction system was studied with fluorine and ferric ion codoped nano-TiO2(nano-F-/Fe3+/TiO2) powders used as the photocatalyst.Effects of initial concentration of thiophene and additional dosage of F-/Fe3+/TiO2 on the reaction rate constant and half-life were investigated.The results showed that the appropriately added dosage of F-/Fe3+/TiO2 was 0.1 g in the 100-mL reaction system and the photooxidative kinetics of thiophene in the presence of F-/Fe3+/TiO2 catalyst was of first-order with a rate constant of 0.6508 h-1 and a half-life of 1.0651 h.The desulfurization rate of thiophene was 98.1%in 5 h and the sulfur content could be reduced from 800 ppm to 15 ppm.The reaction rate constant increased with a decreasing initial concentration of thiophene.

Research on the oxidation kinetics curve of 1Cr11Ni2W2MoV steel hot-dipped Al

In this paper, 1Cr11Ni2W2MoV steel that is aerial engine blade materials was hot dipped Al-6%Si-4%RE in order to improve its application temperature. According to GB/T13303-91 standard, samples with coating and without coating were oxidated at 700℃ from 5 h to 600 h. Two oxidation kinetics curves were drawn in terms of data of tests. The results showed that oxidation resistance of 1Cr11Ni2W2MoV steel hot-dipped Al-6%Si-4%RE is better than one without coating. From SEM and EMPA, the surface of coating formed dense and uninterrupted α-Al2O3, which is the bars of oxidation resistance. In addition, according to one crossing point of the two curves, it was suggested that hot dipped aluminum steel should be annealed before used.

Substrate specificity in the biomimetic catalytic aerobic oxidation of styrene and cyclohexanone by metalloporphyrins: kinetics and mechanistic study

Substrate specificity is a hallmark of enzymatic catalysis.In this work,the biomimetic catalytic oxidation of styrene and cyclohexanone by iron(III)porphyrins and molecular oxygen was carried out,and remarkable differences in efficiency were observed.The specificity of the substrates for biomimetic catalytic oxidation was investigated by kinetics and mechanistic studies.Kinetics studies revealed that the oxidation of styrene followed Michaelis-Menten kinetics with KM=8.99 mol L^(-1),but the oxidation of cyclohexanone followed first-order kinetics with kobs=1.46×10^(-4) s^(-1),indicating that the styrene epoxidation by metalloporphyrins exhibited characteristics of enzyme-like catalysis,while the oxidation of cyclohexanone was in agreement with the general rules of chemical catalysis.Different catalytic mechanisms for the two substrates were discussed by operando electron paramagnetic resonance spectroscopy,operando UV-vis spectroscopy,and KI/starch experiments.Substrate specificity was concluded to be attributed to the stability of high-valence species and oxygen transfer rate.

Evaluating two stages of silicone-containing arylene resin oxidation via experiment and molecular simulation

Silicon-containing aryl acetylene resin(PSA)is a new type of high-temperature resistant resin with excellent oxidation resistance,whereas antioxidant reaction mechanism of PSA resin under ultra-high temperatures still remains unclear.Herein,the oxidation behavior and mechanisms of PSA resin are systematically investigated combining kinetic analysis and Reax FF molecular dynamics(MD)simulations.Thermogravimetric analysis indicates that the oxidation process of PSA resin undergoes two main steps:oxidative mass gain and oxidative degradation.The distributed activation energy model(DAEM)is employed for describing oxidation processes and the best-fit one is obtained using genetic algorithms and differential evolution.DAEM model demonstrates that the oxidative weight gain stage is dominated by two virtual reactants and the oxidative degradation stage consists of three virtual reactants.Correspondingly,the observation of MD reaction pathways indicates that oxygen oxidation of unsaturated structures occurs in the initial stage,which results in the formation of PSA resin oxides.Furthermore,cracked pieces react with O_(2)to generate CO and other chemicals in the second step.The resin matrix's great antioxidation resilience is illustrated by the formation of SiO_(2).The analysis based on MD simulations exhibits an efficient computational proof with the experiments and DAEM methods.Based on the results,a two-stage reaction mechanism is proposed,which provides important theoretical support for the subsequent study of the oxidation behavior of silica-based resins.

Study on metal recovery process and kinetics of oxidative leaching from spent LiFePO_(4)Li-batteries

A green environmental protection and enhanced leaching process was proposed to recover all elements from spent lithium iron phosphate(LiFePO_(4)) lithium batteries.In order to reduce the influence of Al impurity in the recovery process,NaOH was used to remove impurity.After impurity removal,the spent LiFePO_(4) cathode material was used as raw material under the H_(2)SO_(4) system,and the pressure oxidation leaching process was adopted to achieve the preferential leaching of lithium.The E-pH diagram of the Fe-P-Al-H_(2)O system can determine the stable region of each element in the recovery process of spent LiFePO_(4)Li-batteries.Under the optimal conditions(500 r·min^(-1),15 h,363.15 K,0.4 MPa,the liquid-solid ratio was 4:1 ml·g^(-1)and the acid-material ratio was 0.29),the leaching rate of Li was 99.24%,Fe,Al,and Ti were 0.10%,2.07%,and 0.03%,respectively.The Fe and P were precipitated and recovered as FePO_(4)·2H_(2)O.The kinetic analysis shows that the process of high-pressure acid leaching of spent LiFePO_(4) materials depends on the surface chemical reaction.Through the life cycle assessment(LCA)of the spent LiFePO_(4) whole recovery process,eight midpoint impact categories were selected to assess the impact of recovery process.The results can provide basic environmental information on production process for recycling industry.

Oxidation pathway and kinetics of titania slag powders during cooling process in air

The oxidation pathway and kinetics of titania slag powders in air were analyzed using differential scanning calorimetry(DSC)and thermogravimetry(TG).The oxidation pathway of titania slag powder in air was divided into three stages according to their three exothermic peaks and three corresponding mass gain stages indicated by the respective non-isothermal DSC and TG curves.The isothermal oxidation kinetics of high titania slag powders of different sizes were analyzed using the ln-ln analysis method.The results revealed that the entire isothermal oxidation process comprises two stages.The kinetic mechanism of the first stage can be described as f(α) = 1.77(1-α) [-ln (1-α)]^((1.77-1)/1.77),f(α)= 1.97(1-α) [-ln (1-α)]^((1.97-1)/1.97),and f (α) = 1.18(1-α) [-ln (1-α)]^((1.18-1)/1.18).The kinetic mechanism of the second stage for all samples can be described as f (α)=1.5(1-α)^(2/3)[1-(1-α)^(1/3)]^(-1).The activation energies of titania slag powders with different sizes(d_(1)<0.075 mm,0.125 mm<d_(2)<0.150 mm,and 0.425 mm<d_(3)<0.600 mm)for different reaction degrees were calculated.For the given experimental conditions,the rate-controlling step in the first oxidation stage of all the samples is a chemical reaction.The rate-controlling steps of the second oxidation stage are a chemical reaction and internal diffusion(for powders d_(1)<0.075 mm)and internal diffusion(for powders 0.125 mm<d_(2)<0.150 mm and 0.425 mm<d_(3)<0.600 mm).