Kinetic equation for internal oxidation of Cu-Al alloy cylinders

The kinetics of internal oxidation of Cu-A1 alloy cylinders, containing up to 2.214mol% A1, were investigated in the temperature range of 1023 K to 1273 K, and the depth of internal oxidation was measured in the microscopy. A kinetic equation was derived to describe the internal oxidation of Cu-A1 alloy cylinders. For the internal oxidation of Cu-Al alloys employed in the synthesis of alumina dispersion strengthened copper, the kinetic equation can be simplified. The derived equation was checked experimentally by means of oxidation depth measurements and the results show that the derived equation is exact enough to describe the kinetics of internal oxidation of Cu-Al alloy cylinders. Based on this equation and the oxidation depth measurements, the permeability of oxygen in solid copper was obtained. Investigation also shows that there is no evidence for preferential diffusion along grain boundaries in the process of internal oxidation.     

Kinetic Equation for Internal Oxidation of Cu-Al Alloy Spheres

The kinetics of internal oxidation of Cu-Al alloy spheres, containing up to 2.214% mole fraction Al was investigated in the temperature range 1 023 K to 1 273 K, and the depth of internal oxidation was measured in the microscopy. A kinetic equation was derived to describe the internal oxidation of Cu-A1 alloy spheres, which was checked experimentally by means of oxidation depth measurements. The results show that the derived equation is exact enough to describe the kinetics of internal oxidation of Cu-Al alloy spheres. Based on this equation and the oxidation depth measurements, the permeability of oxygen in solid copper has been obtained. Investigation also shows that in the process of internal oxidation, there is no evidence for preferential diffusion along grain boundaries.     

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) ~(2/3)+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)~(1/3). 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.     

Growth kinetics of Thiobacillus ferrooxidans in bioelectrochemical cell

Thiobacillus ferrooxidans might be the most important bacteria used in biometallurgy. The foundation way of its growth process is oxidizing ferrous in order to obtain energy needed for metabolism, but the variation of ferrous concentration and mixed potential of the culture media would have crucial effect on the bacteria growth.Based on the characteristics of Thiobacillus ferrooxidans growth and redox potential of ferric and ferrous, an electrochemical cell was designed conventionally to study growth rule and the relationship between redox potential and bacteria growth was built up, and some growth kinetics of Thiobacillus ferrooxidans were elucidated. It demonstrates that the variation of open potential of electrochemical cell ΔE shows the growth tendency of Thiobacillus ferrooxidans, at the initial growth stage, the value of ΔE increases slowly, when at logistic growth stage, it increases drastically, and the growth rate of bacteria is linear with the oxidation rate of ferrous. The bacteria growth kinetics model is proposed using Monod and Michealis-Menten equation, and the kinetics parameters are got. The consistence of the measured and the calculated results proves that it is proper to use the proposed kinetics model and the electrochemical cell method to describe the growth rule of Thiobacillus ferrooxidans.     

Effect of Al Layer on Oxidation Behavior of NbCrAl Coating

NbCrAl coatings in the presence or absence of Al outer layer were prepared on C103 Nb based alloy and alumina substrate by direct current magnetron sputtering technique. The oxidation performance of coating systems was evaluated by isothermal oxidation tests. The element diffusion and oxidation behavior of the coating systems were investigated. The results indicate that the mass gains of NbCrAl and Al/NbCrAl coatings are 2.02 mg/cm~2 and 0.79 mg/cm~2 at 1 000 ℃ for short time. Al/NbCrAl coatings exhibit more effective protection than NbCrAl coatings. The addition of Al layer can improve the oxidation resistance of NbCrAl coatings, which is attributed to the Al layer offering enough Al content to react with oxygen to form a continuous and dense Al_2O_3 scale on NbCrAl coating and it can inhibit the further internal oxidation.     

Generation reason and corrosion characteristic of cavity of tinplate alloy layer

The surface morphology of alloy layer of tinplate was studied by means of scanning electron microscopy.By using the layer on layer debonding technology of glow discharge spectrum, the contents of C and O at the boundary of alloy layer and black plate were analyzed. And the corrosion characteristic of cavity of tinplate alloy layer was studied on-line and in-situ by means of electrochemical atomic force microscope. The corrosion depth of cavity of alloy layer in-situ after different corrosion time was measured. The results show that the cavity of alloy layer is a critical factor causing rapid decline of corrosion resistance of tinplate, and the formation of cavity of alloy layer is due to incorrect pretreatment of black plate before electrotinning. The cavity of alloy layer is the internal factor causing pitting corrosion of tinplate when the tinplate is applied to food packaging material. And the dynamic equation of pitting corrosion generated in the cavity of alloy layer conforms to logarithm law.     

The active-to-passive oxidation transition mechanism and engineering prediction method of C/SiC composites

This paper studied the active-to-passive oxidative mechanism of C/SiC composite under high temperature and oxidative conditions. An analytic model and computational method were established based on the process of gas diffusion in boundary layer and the equilibrium relations in surface chemical reactions. Simultaneously, an engineering equation to predict the oxygen partial pressure of active-to-passive transition was derived under the specific temperature zone. The results indicated that the active-to-passive oxidation transition of C/SiC is closely related to the composition of the material. At certain temperature and oxygen partial pressure conditions, the composite with high carbon content is prone to cause active oxidation which is negative to the oxidation resistance of the material.     

Dynamic response of cylindrical lined cavity in elastic medium

An analytical solution to the transient dynamic response of a cylindrical lining subjected to an internal loading was presented and the dynamic interaction between the lining and surrounding soil was considered. The lining structure and the soil were treated as a cylindrical elastic shell and an infinite elastic compressible medium, respectively. A two-dimensional axisymmetric wave equation was derived from the governing equation of displacement by introducing the potential functions. Shell equation of motion was established based on continuity conditions. The closed-form solution for dynamic response of the lining due to an impact loading was obtained in Laplace transforms and inverse transforms. Detailed parametric studies were also presented to illustrate the influences of the Poisson ratio of soil, the dynamic shear moduli of both soil and lining and the thickness of lining on dynamic response of the lining.     

Perturbation analysis on post-buckling behavior of pile

The nonlinear large deflection differential equation, based on the assumption that the subsoil coefficient is the 2nd root of the depth, was established by energy method. The perturbation parameter was introduced to transform the equation to a series of linear differential equations to be solved, and the deflection function according with the boundary condition was considered. Then, the nonlinear higher-order asymptotic solution of post-buckling behavior of a pile was obtained by parameter-substituting. The influencing factors such as bury-depth ratio and stiffness ratio of soil to pile, slenderness ratio on the post-buckling behavior of a pile were analyzed. The results show that the pile is more unstable when the bury-depth ratio and stiffness ratio of soil to pile increase, and although the buckling load increases with the stiffness of soil, the pile may ruin for its brittleness. Thus, in the region where buckling behavior of pile must be taken into account, the high grade concrete is supposed to be applied, and the dynamic buckling behavior of pile needs to be further studied.     

The Catalysis of NAD^＋ on Methanol Anode Oxidation Electrode for Direct Methanol Fuel Cell

A tentative idea of developing a liquid-catalytic system on methanol anode oxidation was proposed by analyzing the characteristics of methanol anode oxidation in direct methanol fuel cell. The kinetics of methanol oxidation at a glassy carbon electrode in the presence of nicotinamide adenine dinucleotide ( NAD^ ) was investigated. It is found that the current density of methanol oxidation increases greatly and the electrochemical reaction impedance reduces obviously in the presence of NAD^ compared with those in the adsenee of NAD^ . The catalytic activity of NAD^ is sensitive to temperature. When the temperature preponderates over 45℃, NAD^ is out of fuuction of catalysis for methanol oxidation, which is probably due to the denaturation of NAD^ at a relatively high temperature.     

铜铝合金的氧化分析

研究了铜铝合金内氧化与外氧化的条件，提出了氧化层厚度的动力学模型，研究表明，内氧化过程主要受氧在内氧化层中的扩散系数、氧在金融表面的浓度以及合金溶质含量的影响，外氧化可以通过控制温度和氧分压进行抑制。     

铜铝合金内氧化组织特征的研究

采用包埋法、气体法对不同铝含量的铜铝合金内氧化的组织形貌进行了研究。结果表明，内氧化层的组织形貌主要取决于铝含量。但工艺条件（介质、温度、时间）也有一定的影响。内氧化物的粗化和形态的转变是基体固溶态铝向内氧化层发生了较强逆扩散引起的；内氧化层中铝、氧分布的不均匀性是氧梯度变化与铝逆扩散相互作用的结果。     

Cu－Al粉末烧结合金内氧化研究

用高纯氮气体做介质对Ｃｕ－０．７５％Ａｌ粉末烧结合金进行内氧化处理，用Ｘ－ｒａｙ衍射，ＳＥＭ，ＴＥＭ等分析技术进行研究，结果表明：内氧化物由多相组成，晶内弥散分布的α－Ａｌ＿２Ｏ＿３质点呈球形析出长大；内氧化层中［Ａｌ］，［Ｏ］原子浓度规律分布，反应界面前沿存在［Ａｌ］，［Ｏ］原子浓度的非平衡区，内氧化过程，氧以晶界扩散和体扩散为主，氧化物质点周围Ｃｕ基体的塑性变形，增加了氧原子按位错扩散机制运动的几率；Ｃｕ原子受挤压发生短路迁移充填了邻近区域的空位和晶界缺陷，增加了粉末烧结合金的致密度．     

Influence of nano-scaled dispersed second phase on substructure of deformed dispersion strengthened copper alloy

The deformation behavior of dispersion strengthened copper alloy Cu-Al2O3 was studied by TEM. The results show that nano-scaled dispersed second phase not only increases dislocation density in matrix, but also has an important influence on the dislocation substructure. The presence of fine dispersed Al2 O3 particles results in a uniform and random dislocation distribution in matrix copper and causes the difficulty in formation of dislocation cell structure and the decrease in the amount of cell structure during deformation. Deformation gives rise to much more dislocations and dislocation cells form more difficultly and the decrease in the cell size with the increase of dispersion degree.     

Oxidation kinetics and high temperature in-situ observation of the oxidation behaviour of NbSi_2 at 1023 K

Pest oxidation has been known for a long time in refractory transition-metal disilicides such as NbSi2 and MoSi2[1―4]. However, the origin of pesting reaction of these materials is still under debate. Although the pesting phenomenon in NbSi2 has been reported in several works[5―7], a direct study of the mechanism is scarce at the moment. Compared to NbSi2, pesting in MoSi2 has received relatively extensive attention. Mckamey et al.[8] showed fragmentation near 773K occurred easily in as…     

一种含Ti镍基合金在950℃的恒温氧化行为

用热重分析法测定了氧化动力学曲线,并采用XRD和SEM/EDAX等手段,研究了一种镍基合金950℃的高温氧化行为。结果表明,在950℃氧化初期,合金的氧化质量增重较快,随着氧化时间延长,氧化质量增加的速率逐渐降低,氧化动力学曲线符合抛物线规律,氧化膜出现少量剥落。合金表面氧化膜由三层组成,外氧化层为TiO2,中间层氧化物为Cr2O3、NiCr2O4、CrTiO3和NiAl2O4,内氧化层氧化物为Al2O3.     

不同含量的活性元素钇对K38高温合金1000℃氧化行为的影响

研究添加不同含量活性元素钇（Y）的K38铸造高温合金在1 000℃的氧化行为.结果表明：不添加活性元素Y合金的氧化质量增加明显高于含Y合金.不添加Y的合金和添加0.05%（质量分数,以下同）Y的合金发生了内氧化,内氧化物为Al2O3和TiN.而含0.1%和0.5%Y的合金没有内氧化发生,Y促进了Al的选择性氧化.当Y含量达0.5%时,合金中析出富Y相,降低了合金的氧化抗力.     

Effect of relative density on cyclic oxidation resistance properties of MoSi2

MoSi2 powders were fabricated respectively by mechanical alloying technique and sintering at different temperatures to prepare materials with different relative densities. The relative oxidation behavior of all MoSi2 materials at 1 473 K was investigated by TGA,SEM and XRD. The results show that the ＂pesting＂ is not found in all materials after being oxidized for 480 h. The density has no essential relation to the ＂pesting＂. The oxidation curve of specimens with lower density shows two-step oxidation kinetics. Both the first stage （0-1 h） and the second stage （1-480 h） nearly obey linear kinetics,but the oxidation rates are obviously different. The oxidation kinetics of MoSi2 with higher relative density nearly follows parabolic law. The mass gains of MoSi2 with the lowest relative density （78.6%） and the highest relative density （94.8%） are increased by 10.390 and 0.135 mg/cm^2,respectively. The oxide scale of materials with lower densities is non-protective and makes the oxygen diffusion easy. A dense scale in the material with higher density is formed,which acts as a diffusion barrier to the oxygen atoms to penetrate into the matrix,showing much better high temperature oxidation resistance. The phases distribution of oxidation scale from the outside to the inside is SiO2→Mo5Si3→MoSi2.