多孔碳酸钙陶瓷-人造珊瑚的研究

天然珊瑚有三维贯通的多孔网络结构，它的主要成分碳酸钙(CaCO3)在人体环境可降解。模拟珊瑚的组成与结构，研制新型的组织工程支架材料有着良好的应用前景。本文探索了多孔碳酸钙陶瓷的制备方法，并通过盐析法制备了一种多孔的碳酸钙陶瓷，有望获得高的孔隙率和孔连通性。     

Transport processes during electrowashing of filter cakes

Applications of electric fields during washing of filter cakes increases the removal rate of ions from the cake mother liquor, and under appropriate conditions the field also increases the wash flow rate by electroosmosis. Experimental data that show the key effects of the fields on the rates of ion mass transfer are presented: with the downstream electrode acting as a cathode, cation removal rates are increased whilst the removal rate of the anions is decreased. The concentration profile of the cations with washing time shows an increase in concentration to a value above that of the mother liquor, before it decreases due to displacement by the fresh wash liquor. A model is formulated that describes the advection, dispersion, ion migration and electroosmosis transport processes in the cake. Numerical solution of the model gives cation concentration profiles at the exit of the cake that are in qualitative agreement with the experimental observations. Experimentally measured wash liquor flow rates tend to be lower than what traditional colloid science principles predict by a factor of 5-10: reasons for this difference, supported by experimental work from other researchers, are discussed.     

Preparation of porous carbons from thermoplastic precursors and their performance for electric double layer capacitors

Porous carbons with high surface area were successfully prepared from thermoplastic precursors, such as poly(vinyl alcohol) (PVA), hydroxyl propyl cellulose and poly(ethylene terephthalate), by the carbonization of a mixture with MgO at 900 °C in an inert atmosphere. After carbonization the MgO was dissolved out using a diluted sulfuric acid and the carbons formed were isolated. The mixing of the PVA carbon precursor with the MgO precursors (reagent grade MgO, magnesium acetate or citrate) was done either in powder form or in an aqueous solution. The BET surface area of the carbons obtained via solution mixing could reach a very high value, such as 2000 m²/g, without any activation process. The pore structure of the resultant carbons was found to depend strongly on the mixing method; the carbons prepared via solution mixing were rich in mesopores, but those produced via powder mixing were rich in micropores. The size of mesopores was found to be almost the same as that of the MgO particles, suggesting a way of controlling the mesopore size in the resultant carbons. Measurement of capacitance was carried out in 1 mol/L H₂SO₄ electrolyte. The porous carbon with a BET surface area of 1900 m²/g prepared at 900 °C through solution mixing of Mg acetate with PVA showed a fairly high EDLC capacitance, about 250 F/g with a current density of 20 mA/g and 210 F/g with 1000 mA/g. The rate performance was closely related to the mesoporous surface area.     

PVdF-HFP/P123 hybrid with mesopores: a new matrix for high-conducting, low-leakage porous polymer electrolyte

Highly conducting porous polymer electrolytes comprised of poly(vinylidene-fluoride-co-hexafluoropropylene) (PVdF-HFP), polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide (P123), ethylene carbonate (EC), propylene carbonate (PC), and LiClO₄ were fabricated. The PVdF-HFP/P123 hybrid polymer membranes were made with a phase inverse method and the electrolyte solution uptake was carried out in glove box to avoid the moisture contamination. It was found that when a small amount of polymer surfactant (P123) was blended into the PVdF-HFP, mesopores with well-defined sizes were formed. Impedance spectroscopy showed that the room temperature conductivity of (PVdF-HFP)/P123 polymer electrolytes increased as the content of P123 increased up to 4×10⁻³ S/cm. Nitrogen adsorption isotherms, electrolyte solution uptake, porosity measurements, and SEM micrographs showed that the enhanced conductivity was due to increase the pore volume, pore density, and electrolyte uptake. The highest conduction was found when the weight ratio of P123 to PVdF-HFP was 70%, when big channels were formed in the hybrid polymer membrane. Furthermore, blending P123 in PVDF-HFP reduced the pore size of polymer membrane, therefore, the solution leakage was also reduced. These polymer electrolytes were stable up to 4.5 V (vs Li/Li⁺) and the performance of the model lithium ion battery made by sandwiching the polymer electrolyte between a LiCoO₂ anode and a MCMB cathode, showed great promise for the use of these polymer electrolytes in lithium ion batteries.     

Dynamic modeling of drainage through three-dimensional porous materials

The interplay of viscous, gravity and capillary forces determines the flow behavior of two or more phases through porous materials. In this study, a rule-based dynamic network model is developed to simulate two-phase flow in three-dimensional porous media. A cubic network analog of porous medium is used with cubic bodies and square cross-section throats. The rules for phase movement and redistribution are devised to honor the imbibition and drainage physics at pore scale. These rules are based on the pressure field within the porous medium that is solved for by applying mass conservation at each node. The pressure field governs the movement and flow rates of the fluids within the porous medium. Film flow has been incorporated in a novel way. A pseudo-percolation model is proposed for low but non-zero capillary number (ratio of viscous to capillary forces). The model is used to study primary drainage with constant inlet flow rate and constant inlet pressure boundary conditions. Non-wetting phase front dynamics, apparent wetting residuals (S_wr), and relative permeability are computed as a function of capillary number (N_ca), viscosity ratio (M), and pore-throat size distribution. The simulation results are compared with experimental results from the literature. Depending upon the flow rate and viscosity ratio, the displacement front shows three distinct flow patterns—stable, viscous fingering and capillary fingering. Capillary desaturation curves (S_wr vs. N_ca) depend on the viscosity ratio. It is shown that at high flow rates (or high N_ca), relative permeability assumes a linear dependence upon saturation. Pseudo-static capillary pressure curve is also estimated (by using an invasion percolation model) and is compared with the dynamic capillary pressure obtained from the model.     

A discrete model for non-wetting liquid flow from a point source in a packed bed under the influence of gas flow

A study of non-wetting flow in a packed bed under the influence of gas flow has been carried out. Departing from the usual continuum models, a discrete and deterministic model for liquid flow has been presented to model the liquid flow from single and multiple point sources. Liquid flow is modelled based on force balance approach considering gas drag, bed resistance and gravity forces. Gas flow is modelled using k-ε model for turbulent flow. An X-ray flow visualization technique, developed by our group, is used to study the liquid flow paths in the packed bed. Liquid flow path and velocity has been obtained for various liquid and gas flow rate. Flow paths obtained from the simulation results are in good agreement to those obtained from flow visualization procedure under various conditions. Also, liquid distribution at the bed bottom is reported and compared with the experimental results.     

Enhanced liquid spreading due to porosity

A conceptual pore level model (Chem. Eng. Sci. 57 (2002) 3401) of spreading of liquid over internally wet porous particles is applied to explain reported rector level enhancement in wetting of trickle bed reactor (Ind. Eng. Chem. Res. 36 (1997) 5133). It is confirmed that a symbiotic relationship exists between internal and external wetting of porous particles whereby each enhances the other. Further, it is illustrated that liquid spreading in porous solids is driven more by porosity than by contact angle. A major implication of this phenomena is that liquid will spread more on less wettable (but porous) surfaces in comparison to more wettable (but nonporus) surfaces and a reinterpretation of experiments involving spreading of liquid over porous solids is required. On a large scenario, it is hoped that present exercise will be in important step towards explaining the complex reactor level macro phenomena by simple and conceptual pore level micro models.     

Hollow porous carbon microspheres obtained by the pyrolysis of TiO2/poly(furfuryl alcohol) composite precursors

Disordered carbon materials with high porosity were prepared through the pyrolysis of TiO₂/poly(furfuryl alcohol) composites, obtained by the sol-gel method. The composites were prepared starting from titanium tetra-isopropoxide (TTIP) and furfuryl alcohol (FA) as precursors. Two different synthetic procedures for our composites were carried out, based on the addition of furfuryl alcohol (FA) before or after the TiO₂ nanoparticles formation. Also, different TTIP/FA ratio was tested. The hybrid materials obtained by both synthetic routes were pyrolyzed, under argon flow, at 900 °C producing novel TiO₂/carbon composites. All samples were characterized by XRD, FT-IR, DR-FTIR, Raman spectroscopy and TEM. Results indicated the effective FA polymerization on TiO₂ (anatase) nanoparticles, and polymer conversion to disordered carbon after the pyrolysis, simultaneously with TiO₂ anatase-rutile phase transition. The resulting TiO₂/carbon composites were treated with HF solution aiming the oxide dissolution, yielding an extremely porous carbon material as insoluble fraction. The morphology of these porous carbon materials is strongly dependent on the synthetic route adopted for the composite precursor, varying from carbon foam to highly ordered hollow microspheres.     

多孔介质通道气液两相流型及压降特性研究

通过高速摄影仪研究多孔介质通道内气液两相流体垂直向上流动的流型,在实验参数范围内依次拍摄到泡状流、弹状流、脉冲流、雾状流4种典型流型,并总结了各种流型的特征。依据实验获得的两相流动阻力数据,分别对分相模型阻力关系式和均相模型阻力关系式进行了拟合,得到了适于实验特点的两类阻力关系式。改进后的两类模型均与实验数据实现了较好的吻合,但模型关系式定义中包含了影响阻力压降各要素的均相模型具有更高的预测精度,且该模型物理意义更加清楚,可以优先用于多孔介质通道气液两相流动的阻力计算。     

Effect of gas composition on cementite decomposition and coke formation on iron

Cementite decomposition and coke formation in the metal dusting process of iron were investigated at 700 °C in CO-H₂-H₂O gas mixtures. The presence of graphite deposited on the surface initiates the decomposition of cementite into iron and graphite. The morphology of the reaction products varies with gas composition. For CO concentrations less than 5 vol%, particles of iron or even closed iron layers have been observed at the cementite/graphite interface. With increasing CO content the amount of iron in the interface decreases. At CO concentrations higher than 30 vol%, iron could not be detected at the interface by optical microscopy. Thermo-gravimetric analysis shows that the rate of carbon take-up increases with increasing CO concentration reaching a maximum at about 60-75 vol%.The morphologies of graphite in the coke layer can be identified as three types: porous graphite clusters with embedded iron-containing particles, compact bulk graphite with a uniform thickness and a columnar layered structure, and filamentous carbon with iron-containing phases at the tip or along its length. For gas mixtures with low CO concentrations, e.g. 5 vol%, porous graphite clusters are the main form of carbon although filamentous carbon can be seen at the early stage of reaction. With increasing CO concentrations to, e.g. 30 vol%, a compact bulk graphite is formed on the top of the surface. Under this compact graphite, there is an inner layer of graphite which is the combination of porous graphite clusters and filaments. These two layers of graphite are clearly distinguishable when CO content reaches more than 75 vol%. In this case, the main form of graphite in the inner layer is filamentous carbon. The compact graphite layer suffers a serious deformation and forms many cracks because of the growth of catalytic filamentous carbon underneath. These filaments grow outside from compact graphite crevices and finally cover the whole surface. The higher the CO content in the gas, the more the tendency of filamentous carbon formation. The interplay between morphologies of carbon formation and metal dusting has been discussed.