Ablation mechanism of WC-SiC double layer coating under oxyacetylene torch test

A WC-SiC double-layer coating was prepared on C/C composites to improve their anti-ablation property. The WC outer layer was designed to withstand high heat flux by its high mechanical strength, the SiC inner layer could transform into SiO₂ to block oxygen by its good anti-oxygen permeability. During ablation process, amounts of SiO₂ filled into the pores and cracks of WC outer layer, forming a steadily self-filling and cooling structure. As a result, the mass and linear ablation rates of WC-SiC coated C/C composites were 0.013 mg s⁻¹ cm² and −1.61 µm/s, respectively. Compared with single SiC coated and single WC coated C/C composites, the linear ablation rates decreased by 46.3% and 27.3%, respectively, indicating that WC-SiC coating has a remarkable effect to resist chemical and mechanical ablation.     

Oxygen diffusion at surface reduction in catalysts for selective oxidation

The coefficient of oxygen diffusion and the activation energy for diffusion have been measured for the series of oxide catalysts of selective oxidation of organic compounds (Sm-Mg-O, Sm-O; V-P-O, Sn-Sb-O, Sn-Bi-O, Fe-Sb-O, Bi-Sb-O). The rates of oxygen diffusion under catalytic conditions have been compared with the reaction rates. For all studied systems (except Sm-O and Sm-Mg-O) at optimal operative temperatures the maximum rate of oxygen diffusion is sufficient to carry out the reactions of selective oxidation through rapid oxygen diffusion in the surface layers.     

Estimation of surface diffusion coefficient in liquid phase adsorption

An estimation procedure of surface diffusion coefficient, D_s, in liquid phase adsorption was proposed. The procedure is based on a restricted diffusion model, in which D_s is correlated with molecular diffusivity by considering a restriction energy due to an adsorptive interaction between adsorbates and adsorbents. In some adsorption systems, D_s of different adsorbates could be calculated with an error less than about 50% from only one datum of each adsorption equilibrium constant. Irrespective of temperature, the procedure, can be applied for the estimation of D_s even in a wide range of D_s of about 4 orders of magnitude.     

Duplex ceramic coating produced by low temperature thermo-reactive deposition and diffusion on the cold work tool steel substrate: Thermodynamics,kinetics and modeling

Specimens of DIN 100MnCrW4 steel (type O1 tool steel) have been cut and prepared for performing a duplex surface treatment involving nitriding and low temperature vanadium thermo-reactive deposition and diffusion (TRD) technique. The TRD process was performed in a molten salt bath at different temperatures of 575, 650 and 725 °C for 1–30 h. The treatment formed a vanadium carbonitride coating with the thickness up to 10.5 μm on a hardened diffusion zone. Characterizations by means of an optical microscope (OM), scanning electron microscope equipped with energy dispersive X-ray spectrometer (SEM–EDS) and X-ray diffraction analysis (XRD) indicated that the compact and dense coating mainly consisted of V(C,N) and V₂(C,N) phases. All the growth processes of the formed vanadium carbonitride layer obtained by TRD followed a parabolic kinetics while the calculated activation energy (Q) for the treatment was 181.1 kJ/mol. An artificial neural network (ANN) based model for predicting the layer thickness of ceramic coatings was presented. Constructing the model, training, validating and testing of experimental results from 72 different specimens were conducted. The data used as inputs in the proposed model were arranged in a format of five parameters that comprised of “pre-nitriding time”, “ferro-vanadium particle size”, “ferro-vanadium weight percent”, “salt bath temperature” and “coating time”. Accordingly, the thickness of duplex coating in each specimen was estimated accurately. Finally, the proposed ANN-based model showed a strong potential for predicting the layer thickness of duplex ceramic coating performed by the TRD technique on the substrate of cold work tool steel.     

Film‐surface diffusion during the adsorption of acid dyes onto activated carbon

A mass transport model has been developed and applied to the adsorption of three acid dyes onto activated carbon in three single component systems. The mass transfer model is based on two rate controlling mass transfer steps, namely external film mass transfer and homogeneous solid‐phase surface diffusion (HSD). Almost all previous film‐HSD models have been based on numerical solutions to the diffusion equation using orthogonal collocation or Crank–Nicolson finite difference solutions. However, in the present model a semi‐analytical solution to the solid surface diffusion equation is presented, yielding a sophisticated solution of the differential equations. The solutions provide a good correlation between the experimental concentration–time decay curves by incorporating the Langmuir equilibrium isotherm to describe the solid phase surface dye concentrations. However, the surface diffusivities show a dependence on the carbon particle surface coverage and these diffusivities have been correlated using a Darken relationship. Copyright © 2004 Society of Chemical Industry     

Study of oxygen diffusion in MgO in the process of surface reduction

We have defined the coefficient of oxygen diffusion in MgO (S _spec = 55 m²/g) at 750 ° and 780 °C, the activation energy for diffusion by measuring oxygen diffusion rates at different degrees of surface reduction. The method used for defining the oxygen diffusion rate is based on the increase in the rate of oxide catalyst reduction (CO or H₂) after keeping the sample in vacuum.     

高铁浓度下氧化亚铁硫杆菌的生长动力学

通过改变初始Fe2 浓度,对氧化亚铁硫杆菌生长过程中的代谢变化进行了研究。依据产物抑制的Monod方程,推导并建立了氧化亚铁硫杆菌在高铁浓度下的生长动力学方程。实验结果表明:随着Fe2 浓度的增加,底物抑制作用增加,导致细菌对底物的亲和力减小,Ks值增大。细菌比生长速率的实验值和模拟值之间的相关系数为0.97,表明该动力学方程能够较好地描述高铁浓度下氧化亚铁硫杆菌的生长情况。     

Effect of mono and hybrid ceramic reinforcement particles on the tribological behavior of the AZ31 matrix surface composites developed by friction stir processing

The effects of the size and morphology of the reinforcement particles on hardness and tribological behaviors of the AZ31 Mg alloy matrix composites were studied. Different ceramic compounds, including boron carbide (B₄C), tungsten carbide (WC), and Zirconia (ZrO₂) were selected as the reinforcement materials for developing mono composites. The average sizes of the B₄C, WC, and ZrO₂ particles were about 150 μm, 5 μm, and 35 nm, respectively. Besides, hybrid reinforcements composed of the B₄C + ZrO₂ and WC + ZrO₂ powders were employed to develop hybrid composites. All the composite were fabricated using the friction stir processing (FSP) technique. Investigating the microstructure of the composites by secondary electron microscopy (SEM) analysis showed a homogenous distribution of the reinforcement particles in the AZ31 Mg alloy matrix. Microhardness measurements revealed that the hardness of AZ31/ZrO₂ nanocomposite is about 120% higher than that of AZ31 base metal. According to the results of the dry sliding wear tests, the AZ31/B₄C and AZ31/ZrO₂ composites had a maximum wear resistance and a minimum friction coefficient average, respectively. Combining the B₄C and WC reinforcements with the ZrO₂ nanoparticles caused an improvement in wear resistance and friction performances of the hybrid composites. SEM observations of the worn surfaces and debris resulted from wearing of the samples after 500 m sliding distance under the normal load of 10 N, revealed that the severe and mild abrasive mechanisms are dominant.     

Evaluation of effective diffusivity of adsorbate in the absence of adsorption and surface diffusion

A method is suggested for the evaluation of effective diffusivity of adsorbate in the absence of adsorption and surface diffusion, the precise value of which is required for estimating the effective surface diffusivity and the extent of influence of adsorption on the overall mass flux in a porous solid. The method does not require the knowledge of tortuosity factor, the accurate values of average pore radius for micro, transitional and macro pores, or the porosities corresponding to micro and macro pores, which are required in case of diffusion in the transitional region and in the solids containing bimodal pore size distribution.     

Application of the concentration-dependent surface diffusion model on the multicomponent fixed-bed adsorption systems

The ability of bone char to adsorb three metal ions, namely, cadmium, copper and zinc, from effluents in fixed beds has been studied. Two binary metal ion sorption systems, Cd+Cu and Cu+Zn, have been investigated. The variables studied include metal ion solution flowrate, initial metal ion concentration, and bone char particle size bed height. The experimental breakthrough curves for each binary system were measured at five bed heights.A multicomponent film-surface diffusion model has been developed to predict the breakthrough curves by incorporating the IAS for both the Langmuir and the Sips equations, since they both correlate the single component equilibrium isotherm data well. A novel development is the modification of the solution methodology, previously restricted to a constant diffusivity, to incorporate a variable diffusivity correlated with adsorbent coverage by the constant self-diffusivity. The self-diffusivities for the metal ions have been evaluated.     

Investigation of mass transport in gas diffusion layer at the air cathode of a PEMFC

In a polymer electrolyte membrane fuel cell (PEMFC), slow diffusion in the gas diffusion electrode may induce oxygen depletion when using air at the cathode. This work focuses on the behavior of a single PEMFC built with a Nafion^® based MEA and an E-TEK gas diffusion layer and fed at the cathode with nitrogen containing 5, 10 and 20% of oxygen and working at different cell temperatures and relative humidities. The purpose is to apply the experimental impedance technique to cells wherein transport limitations at the cathode are significant. In parallel, a model is proposed to interpret the polarization curves and the impedance diagrams of a single PEMFC. The model accounts for mass transport through the gas diffusion electrode. It allows us to qualitatively analyze the experimental polarization curves and the corresponding impedance spectra and highlights the intra-electrode processes and the influence of the gas diffusion layer.     

Effect of tungsten carbide,silicon carbide and graphite particulates on the mechanical and microstructural characteristics of AA 5052 hybrid composites

Reinforced aluminium metal matrix composite materials are being used extensively in diverse fields that include aerospace and automobile. In this investigation, we introduce two distinct and novel types of aluminium hybrid composites and characterize their mechanical properties and microstructure. The first type was fabricated by reinforcing aluminium alloy (AA 5052) with tungsten carbide (WC) and graphite particulates and the second type was fabricated by reinforcing AA 5052 with silicon carbide (SiC) and graphite particulates. The composite material was processed through the melt-stir casting method and characterized by analyzing their densities, micro hardness, Charpy impact strength, tensile strength and peak elongation. Melt-stir casting method was chosen due to its cost effectiveness and productivity. Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) studies were conducted to analyze thorough mixing of the reinforcements in the aluminium matrix metal. It was found that addition of tungsten carbide and graphite particulates with AA 5052 resulted in an increase in micro hardness and Charpy impact strength by 10.3% and 34.2% respectively, which are found to be better when compared to that of adding SiC and graphite particulates with AA 5052. Moreover, tensile tests revealed that there was a drop in tensile strength for the Al/SiC/graphite composites, while the peak elongation increases for both composites. On the other hand, while adding WC and graphite particulates the tensile strength of the composite improved by 15.12%. Also, the SEM fractographs taken for Al/SiC/graphite composite samples, subjected to Charpy impact and tensile tests revealed the presence of particle fractures and cracks and confirmed the possibility of plastic deformation. The results showed the Al/WC/graphite composites to be the superior among the two fabricated composites in terms of mechanical properties and therefore have good potential for structural applications.     

The effects of lignocellulosic fiber surface area on the dynamics of lignin oxidation and diffusion

A novel preliminary experimental approach was developed to determine the effect of maximizing pulp fiber surface area for the regulation of the oxidation and diffusion of lignin through the carbohydrate matrix. The approach entailed liquid nitrogen freezing of mature black spruce kraft pulp fibers and subsequent mechanical grinding to a fine powder to test the effect of enhanced pulp fiber surface area on the efficiencies of lignin oxidation and lignin diffusion. It was found that the liquid nitrogen ground pulp samples provided higher optical reflectance (brightness) after both oxygen and hydrogen peroxide oxidation, which appears to be from chromophoric (chemical) differences and not light scattering differences as supported by UV/Vis spectroscopy. BET (absorption) experiments indicated a dramatic difference in the surface area of the pulp as a result of the grinding, although no differences existed among the pore sizes between the samples, as determined from SEM experiments. Lignin diffusion experiments demonstrated that differences did exist in the kinetics of lignin diffusion into a bulk solution between a control and liquid nitrogen ground samples. Lignin uptake into bulk solutions was enhanced by the liquid nitrogen/pulp‐grinding technique albeit not from chemical changes in the lignin because the subsequent NMR spectra did not point to any major chemical differences as a result of liquid nitrogen freezing and grinding. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 177–181, 2004     

Influence of talc genesis and particle surface on the crystallization kinetics of polypropylene/talc composites

Talc is a laminar silicate, considered as an excellent nucleating agent for polypropylene (PP) crystallization. However, properties of PP/talc composites depend on the morphology, size, and surface of mineral particles. In this sense, talc from several ores, having different morphology, imparts specific characteristics on these materials. Also, taking into account that PP‐talc adhesion is not necessarily good due to the apolar character of PP, talc surface has been modified in order to increase this parameter. In this work, the effects of talc genesis, geomorphologic aspects, and particle surface characteristics on crystallization of PP/talc composites are analyzed. Isothermal crystallization of PP/talc composites was studied by using differential scanning calorimetry, based on Avrami model. The final crystalline morphology of talc‐filled PP was analyzed by means optical microscopy. The results show that the blocky talc morphology favors even more the crystallization compared to the platy one, at the same particle size. Taking into account the surface treatment studied in this work, the talc surface is made hydrophobic and the particle delamination is favored. As a consequence, so‐modified talc is very effective in increasing the crystallization temperature of PP and the nuclei number that grow during the crystallization with respect to the untreated talc. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Role of microstructure reactivity and surface diffusion in explaining flash (ultra-rapid) sintering kinetics

The competition between sintering and coarsening is cited by numerous authors as one of the potential factors for explaining the ultra-rapid sintering kinetics of flash sintering. In particular, surface diffusion is a mechanism decreasing the driving force of sintering by changing the initial highly reactive microstructures (particle contact) into poorly reactive porous skeleton structures (spherical porosity). We show by finite element simulations that flash SPS experiments high specimen temperatures close to 2000 °C. These high temperatures are not sufficient to explain the ultra-rapid sintering kinetics if typical spherical pore theoretical moduli are employed. On the contrary, reactive experimentally determined moduli succeed in explaining the ultra-rapid sintering kinetics. Mesoscale simulations evidenced that the origin of such reactive experimental moduli is a porous skeleton geometry with a significant delay in surface diffusion and particle rearrangement. This highlights the important role of the surface diffusion negation (favoring higher stress intensification factor) in flash sintering.     

Determination of the kinetics of diffusion in coals by solvent swelling techniques

A simple technique has been developed for measuring the kinetics of solvent diffusion in coals at various temperatures. The technique is based on a well-known method for measuring the volumetric swelling of coals by solvents. Several coals have been examined in both pyridine and tetrahydrofuran, at temperatures between 298 and 332 K. The diffusion follows the well-established case II rate law at ambient temperatures, implying that the processes are controlled by relaxation in the coal network structure. As temperatures are increased, the process becomes more Fickian in nature. The activation energies for the diffusion-relaxation processes are in the range 31 to 82 kJ mol⁻¹.     

The importance of diffusion in surface reactions demonstrated with STM

We have used STM to observe directly a process which can be described as two-dimensional, surface-mediated Ostwald ripening, occurring during the decomposition of methoxy intermediates on a Cu(l10) surface. Some islands get bigger during the course of the reaction, at the expense of smaller ones, and it is shown that this diffusion is important for dictating the rate of methanol decomposition. This is proposed to occur from the dilute phase of methoxy existing in the inter-island region and the methoxy maintains a pseudo steady state there, supplied by diffusion from, and between, islands of adsorbate on the surface.     

影响镁碳耐火材料表面MgO致密层形成的因素

研究了镁碳耐火材料中镁砂原料的种类和碳含量 ,渣剂的有无及碱度 ,炉内气氛以及是否加铝脱氧等因素对镁碳耐火材料表面MgO致密层形成的影响。结果表明 :(1)在w(C) =10 %～ 2 0 %范围内 ,随着碳含量的降低 ,形成的MgO致密层越完整 ,且厚度增加 ;(2 )Mg(g)氧化形成MgO致密层的氧是由熔渣通过熔融金属提供的 ,凡是影响熔渣和熔融金属中氧活度的因素 ,都会对MgO致密层的形成产生影响 ;(3)炉内气氛对MgO致密层的形成没有明显的影响 ;(4)与电熔镁砂相比 ,使用烧结镁砂为原料时 ,耐火材料表面更容易形成MgO致密层。     

An equivalent diffusion coefficient model of the oxidation of ceramic matrix composites

A multiscale analysis method was developed to simulate the reaction-diffusion process of SiC/SiC composite structures in a coupled thermo-chemo-mechanical environment. For the diffusion process, the airflow channel was characterized by an equivalent diffusion coefficient model, which was established in this study. The corresponding calculation was developed using a numerical analysis method to obtain the gas concentration distribution in the structure. For the reaction process, an oxidation kinetics model was adopted to calculate morphological evolution of the airflow channel. The equivalent diffusion coefficient was then updated, and the reaction–diffusion coupling calculation was performed through an iterative scheme. To validate the model, an oxidation tensile test was conducted at 1200 °C. Finally, an adjustment sheet model was calculated as an example to analyze its reaction-diffusion process, proving that this method can be applied to SiC/SiC components under complex aerodynamic and temperature loads.     

Research into the kinetics of COS elimination from syngas at moderate temperatures

Thermogravimetry at constant temperature and programmed temperatures is used to study reaction kinetics and possible mechanism of COS desulfurization using ferric oxide as the main active component. The apparent reaction activation energy is smaller in hydrogen atmosphere than in nitrogen. The desulfurization reaction of COS takes place easily in a hydrogen atmosphere. At the same time, the influence of the reducing temperature on the desulfurizing reaction was also studied in the TGA apparatus and was shown to play an important part for ferric desulfurization. The optimum temperature for the reducing reaction is under 360 °C. The kinetics of the COS removal reaction are approximately first-order. When the reaction gas contains hydrogen, the apparent reaction activation energy is 12.36 kJ mol⁻¹, in contrast to 21.92 kJ mol⁻¹ in the absence of hydrogen.