氮化硅结合碳化硅耐火材料的氧化

氮化硅结合碳化硅耐火材料高温氧化后，其抗折强度有所提高，但经扫描电镜观察，材料断面结构已发生了明显的变化。该材料长时间在氧化气氛中使用，可靠性将下降。     

Processing and microstructure-permeation properties of silica bonded silicon carbide ceramic membrane

Porous SiC is a valuable membrane material for the microfiltration and ultrafiltration of various wastewaters because of its high hydrophilicity and low fouling tendency, but its preparation has been limited by the high sintering temperature. Here, a silica bonded silicon carbide membrane was prepared by the oxidation of SiC at low temperature. When the SiC substrates were sintered in the temperature range from 1200 to 1400℃, their porosity decreased from 45 % to 37 % while the flexural strength increased from 45 to 59 MPa. For the selective layers made from SiC particles with 0.5 μm in diameter, the average pore sizes that sintered at 1050 and 1150 ℃ were 0.34 and 0.26 μm, respectively, corresponding to the water fluxes of 1080 and 1240 L/(m² h, respectively. Thus, this technique provided a cost-effective path to prepare ceramic membrane at low sintering temperature.     

Tuning microstructures and separation behaviors of pure silicon carbide membranes

This study reports the preparation of silicon carbide ceramic membranes with pure silicon carbide particles without sintering aids. The effects of sintering temperature on the microstructure, mechanical and filtration properties were investigated. The porosity of the substrate layer increased from 37% to 41% when the sintering temperature ranged from 2150 to 2300 °C, whereas the flexural strength increased from 14.5 to 18.2 MPa. The separation layer was coated on the substrate layer using a spray process. When sintered at 1850 °C, a smooth and defect-free layer was formed with an average pore size and layer thickness of 1.2 and 60 μm, respectively. With the increase of average pore size, the filtration flux increased from 2650 to 2800 L/(m² h bar). Such ceramic membranes can be used to separate corrosive wastewater and high-temperature wastewaters owing to the exclusion of sintering aids, unlike the conventional ceramic membranes.     

Bio-inspired modification of silicon carbide foams for oil/water separation and rapid power-free absorption towards highly viscous oils

A bio-inspired strategy for the fabrication of superhyrophobic silicon carbide (SiC) ceramic foams (SCFs) using commercially available melamine foam (MF) as the template and vinyl-containing hyperbranched liquid polycarbosilane (VHPCS) as the binder was developed. The pre-oxidation process and crystallization degree during the sintering were monitored by Fourier transform infrared spectroscopy and X-ray diffraction. A plausible reaction was proposed and the thermogravimetry analysis results indicated that VHPCS was more suitable for the adhesive agent of SiC powders. By optimizing the mass ratio of VHPCS and SiC, a maximum compression strength of 1.25?MPa for SCFs was achieved with a low density of 0.514?g/cm³ and only 6.72% of volume shrinkage. The obtained SCFs exhibited rapid power-free absorption towards highly viscous oils after a biomimetic surface modification with n-octadecylamine (ODA). It took only 22?s for the complete absorption of 200?μL ultra-high viscosity oil (5000?mPa?s). A probable mechanism for the rapid absorption of viscous oil had been revealed and the decoration of low-surface-energy molecules together with the distinct porous structure were regarded as the critical factors.     

A TiO2 modified whisker mullite hollow fiber ceramic membrane for high-efficiency oil/water emulsions separation

Design and preparation of membranes with ultrahigh separation performance and antifouling property for oil-in-water (O/W) emulsions remains challenging. In this study, a high flux mullite/TiO₂ ceramic composite membrane was prepared via multi-precipitation of TiO₂ on a whisker mullite hollow fiber support synthesized by combining phase inversion and high-temperature sintering techniques. The results showed that the generated whisker mullite structure improved the permeation flux, and the micro-nano structured TiO₂ functional layer endowed the membrane surface with superhydrophility and stability. The retention of the optimal composite membrane (M20T13) that was soaked in the titanium solution 20 times for 13 min each time for the O/W emulsions like n-hexane, toluene and engine oil maintained over 98 %, and the flux after 6 h filtration was 668.34 L·m⁻²·h⁻¹, 487.25 L·m⁻²·h⁻¹ and 258.66 L·m⁻²·h⁻¹, respectively, much higher than that of the optimal substrate (F3A1, mass ratio of fly ash: Al₂O₃ = 3:1). Moreover, the flux recovery rate of M20T13 was much higher than that of F3A1 after chemical backwashing. This work manifests great potential in O/W treatment fields.     

Preparation and characterization of polyvinylidene fluoride hollow fiber membranes for ultrafiltration

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared using the solvent spinning method. N,N-dimethylacetamide was the solvent and ethylene glycol was employed as non-solvent additive. The effect of the concentration of ethylene glycol in the PVDF spinning solution as well as the effect of ethanol either in the internal or the external coagulant on the morphology of the hollow fibers was investigated. The prepared membranes were characterized in terms of the liquid entry pressure of water measurements, the gas permeation tests, the scanning electron microscopy, the atomic force microscopy, and the solute transport experiments. Ultrafiltration experiments were conducted using polyethylene glycol and polyethylene oxides of different molecular weights cut-off as solutes. A comparative analysis was made between the membrane characteristic parameters obtained from the different characterization techniques.     

Crosslinking kinetics of polycarbosilane precursor in ozone atmosphere and the formation mechanism of continuous hollow SiC fiber

Crosslinking is favorable for increasing the ceramic yield of polycarbosilane precursor (PCS), so PCS fiber with crosslinked skin-uncrosslinked core structure may contribute to formation of hollow SiC fiber. In this study, diffusion-controlled ozone oxidation crosslinking method was adopted. EDS verified the oxygen element contributing to crosslinking mainly distributed in the outer layer of ozone-crosslinked PCS fiber (O ? PCS_f). After pyrolysis, SEM confirmed the formation of continuous hollow fiber and XRD indicated the presence of β-SiC structure. N₂ adsorption-desorption measurement demonstrated that a lot of micropores and mesopores, which were the main escape paths for degradation product of uncrosslinked core part of O ? PCS_f and contributed to the formation of continuous hollow SiC fiber, formed along fiber during pyrolysis and disappeared after the pyrolysis temperature was increased. In addition, by adjusting ozone oxidation time and applying vacuum pyrolysis method, the morphology of resulting hollow SiC fiber could be further modified.     

Oxygen permeation study of perovskite hollow fiber membranes

The first oxygen permeation data of a dense hollow fiber perovskite membrane based on BaCo_xFe_yZr_zO_3 − δ are reported. The hollow fiber was prepared by a phase inversion process. Dense fibers were obtained with the following typical geometries: outer diameter, 800–900 μm; inner diameter, 500–600 μm; length, 30 cm. The O₂-permeation through the hollow fiber perovskite membrane was studied in a high-temperature gas permeation cell under different operation conditions. The increase of the helium gas flow rate reduces the oxygen partial pressure (p_O2) on the core side and a higher oxygen permeation flux is observed. High oxygen flux of 0.73 m³ (O₂)/(m² (membrane) h) was achieved at 850 °C under the operation parameters F_air (shell side) = 150 ml/min and F_He (core side) = 30 ml/min. The oxygen partial pressure dependence of the O₂ permeation flux indicated an interplay of both surface reaction and bulk diffusion as rate limiting steps. During 5 days of permeation a high and stable oxygen flux was observed. X-ray diffraction patterns of fresh and spent membranes after the permeation measurements revealed that no degradation after oxygen permeation appears.     

Influence of mechanical activation on combustion synthesis of fine silicon carbide (SiC) powder

The influence of mechanical activation of powder mixtures of Si and C, via high energy attrition milling (up to 12 h), on combustion synthesis of SiC was experimentally investigated. β-SiC fine powder was successfully fabricated in 1.0 MPa N₂ atmosphere without other additional treatments, such as preheating, electric action, or chemical activation. Relatively weak peaks of α-SiC, α-Si₃N₄ and Si₂ON₂ were also found in the final products. The experimental results and their theoretical treatment showed that mechanical activation via high energy ball-milling provides to the initial Si/C powder mixture extra energy, which is needed to increase the reactivity of powder mixture and to make possible the ignition and the sustaining of combustion reaction to form SiC.     

Application of asymmetric Si3N4 hollow fiber membrane for cross-flow microfiltration of oily waste water

The asymmetric morphology of silicon nitride (Si₃N₄) ceramic hollow fiber membrane with a selective spongiform outer layer was optimized by the air gap distance and the internal rate of coagulate for oil/water emulsion microfiltration. The effect of trans-membrane pressure (TMP), feed flow rate (FFR), and pH of the feeding emulsion on the separation performance were determined experimentally. Membrane fouling has increased by dissociation of oil droplets during filtration at high TMP and FFR values. Fouling phenomena were studied based on standard pore blocking model. The pH by affecting the surface charge of the Si₃N₄ hollow fibers and zeta potential of the feed emulsion has also been introduced as a prominent influential factor on separation efficiency. The highest values of permeate flux (390 Lm^?2h^-1) and oil rejection (95%) were recorded in alkaline pH. The fabricated Si₃N₄ ceramic membranes were completely recovered (≤99%) by simple thermal treatment at 400 °C.     

Zirconia ultrafiltration membranes on silicon carbide substrate: microstructure and water flux

This study reported the preparation of ZrO₂/SiC ceramic membrane with silicon carbide as the substrate and intermediate layers and zirconia as the selective layer. The substrate and intermediate layers were sintered by evaporation-condensation process at 2200 and 1900 ℃, respectively. After sintering, the intermediate layer presented layer thickness of 50 μm, pore size of 0.87 μm and pure water permeability of 2140 L/(m²·h). The selective lay was deposited on the silicon carbide substrate by dip-coating method and then sintered in the temperature range from 800 to 1000 ℃. For the membrane coated by one dip-coating cycle and sintered at 800 ℃, it presented average pores of 82 nm and water flux of 850 L/(m²·h). Due to the exclusion of low-melting oxides during sintering, the ZrO₂/SiC ceramic membrane can satisfy the separation and purification of chemical corrosion and high temperature wastewater.     

Cobalt-free SrFe1−xMoxO3-δ perovskite hollow fiber membranes for oxygen separation

SrFe_0.95Mo_0.05O_3-δ (SFM5) perovskite hollow fiber (HF) membranes with a finger-like structure were fabricated by a phase inversion technique. The oxygen flux through SFM5 hollow fiber membrane was evaluated and reached 0.64 μmol/cm² *s at T = 880 °C, which is 5 times higher than that of a disk SFM5 membrane (0.12 μmol/cm² *s). A further increase in oxygen fluxes was attained by Ag deposition on the inner surface of SFM5 hollow fiber membrane. The oxygen flux of SFM5 HF membranes is governed by surface-exchange reactions on the permeate side. The equilibrium "3 − δ − lg pO₂ − T" diagrams showed that doping of SF by molybdenum leads to a broadening of the cubic perovskite phase stability region.     

Corrosion resistance of silicon-infiltrated silicon carbide (SiSiC)

Silicon carbide ceramics have found widespread use due to their high corrosion stability. Both solid state-sintered silicon carbide, which has an extremely high corrosion resistance, and silicon-infiltrated silicon carbide are used for various applications. The latter material contains SiC as well as free silicon, which is less stable. Hence, in the present work, the corrosion behavior of silicon-infiltrated silicon carbide ceramics was investigated in NaOH solutions. Long-term corrosion experiments were conducted, and a method for analyzing the corrosion behavior in short-term experiments was developed. The short-term method is based on the accurate measurement of the corrosion depth by laser scanning microscopy on polished surfaces. The results of both methods were in good agreement. The advantage of the short-term method is that it provides information on changes in corrosion mechanisms and corrosion rates in the initial period and as a function of the impurities present. Preferential corrosion of Si at the interface to SiC was observed. TEM investigations revealed that this enhanced corrosion was caused by the segregation of impurities.     

Mechanical analysis of hollow fiber membrane integrity in water reuse applications

In order to gain insight into membrane fiber failure (i.e., loss of integrity), properties of five hollow fiber membranes and four hollow fiber modules were evaluated. Specifically, membrane material, membrane symmetry, fiber modulus of elasticity, fiber diameter and thickness, module potting technique, module flow pattern (inside-out or outside-in), and coliform breakthrough were investigated. The approach combined evaluation of the above properties with mathematical modeling of structure-fluid interactions to comprehensively evaluate the properties most important for maintaining hollow fiber membrane integrity. Tensile strength testing revealed that the strongest fiber was an asymmetric polyacrylonitrile membrane fiber. The weakest fiber was a symmetric polyethylene membrane fiber. Pilot plant testing on the four membrane modules revealed that membrane symmetry may be a more important factor than potting technique for hollow fiber integrity. Results from the SEM and tensile testing were used as input to a finite element analysis model used to evaluate time-dependent structure-fluid interactions. It was found that additional stresses at the juncture of the potting material and the hollow fiber membranes exist. These stresses likely lead to the formation of fractures.     

碳化硅纤维的开发与应用进展

介绍了碳化硅纤维的性能、制备、应用及其现状与发展趋势。     

Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes for pervaporation separation of ethanol/water solution

Polysulfone (PSF) hollow fiber membranes were spun by phase‐inversion method from 29 wt % solids of 29 : 65 : 6 PSF/NMP/glycerol and 29 : 64 : 7 PSF/DMAc/glycol using 93.5 : 6.5 NMP/water and 94.5 : 5.5 DMAc/water as bore fluids, respectively, while the external coagulant was water. Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes were prepared after PSF hollow fiber membranes were coated using different PVA aqueous solutions, which were composed of PVA, fatty alcohol polyoxyethylene ether (AEO₉), maleic acid (MAC), and water. Two coating methods (dip coating and vacuum coating) and different heat treatments were discussed. The effects of hollow fiber membrane treatment methods, membrane structures, ethanol solution temperatures, and MAC/PVA ratios on the pervaporation performance of 95 wt % ethanol/water solution were studied. Using the vacuum‐coating method, the suitable MAC/PVA ratio was 0.3 for the preparation of PVA/PSF hollow fiber composite membrane with the sponge‐like membrane structure. Its pervaporation performance was as follows: separation factor (α) was 185 while permeation flux (J) was 30g/m²·h at 50°C. Based on the experimental results, it was found that separation factor (α) of PVA/PSF composite membrane with single finger‐void membrane structure was higher than that with the sponge‐like membrane structure. Therefore, single finger‐void membrane structure as the supported membrane was more suitable than sponge‐like membrane structure for the preparation of PVA/PSF hollow fiber composite membrane. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 247–254, 2005     

以水玻璃为硅源喷雾干燥制备SiC前驱体

以廉价的水玻璃和炭黑为原料,通过制备均匀混合的前驱体,利用碳热还原反应合成出超细SiC粉体。比较研究了前驱体喷雾干燥与搅拌干燥两种制备方法对体系碳热还原反应的影响,重点考察了喷雾干燥制备过程中主要工艺参数对前驱粉体密度及收率的影响。结果表明:喷雾制备的前驱体具有更高的反应活性,在1550℃下反应2h就可使SiO2转化率达到89.4%,搅拌干燥制备的前驱体转化率只有65.2%。喷雾干燥过程中,适当提高进口温度、喷雾头转速并降低料液的固体含量,可获得高收率、高产率的前驱粉体,利于整个制备工艺生产效率及产率的提高。     

Poly(vinyl chloride) (PVC) hollow fibre membranes for gas separation

Poly(vinyl chloride) (PVC) gas separation hollow fibre membranes were produced from multicomponent dopes using dry/wet forced convection spinning. Membranes spun from a low polymer content solution exhibited disappointing gas separation properties. Their low selectivities were indicative of thick skins and high surface porosities. In contrast, high polymer content spun fibres showed good gas separation properties. Selectivities were high, active layers relatively thin and surface porosities moderate. Coating with poly(dimethylsiloxane) nullified the surface pores. The favourable performance of the high polymer content spun fibres was also related to shear rate and forced convection residence time during spinning. To the knowledge of the authors, this work represents the first reported success in producing PVC hollow fibre membranes with morphologies suitable for gas separation. The development of PVC hollow fibres relates to the ultimate quest to produce membranes capable of reliably separating oxygen and ozone gas mixtures.     

Hydrophilic hollow fiber membranes for water desalination by the pervaporation method

Hydrophilic ion-exchange membranes based on sulfonated polyethylene hollow fibers were manufactured, and their suitability for a water pervaporation process was studied for possible application in water desalination systems. The effects of the following parameters on the average water flux were determined: membrane properties (diameter (0.4–1.8 mm) and wall thickness (0.05–0.18 mm)); charge density (0.6–1.2 meq g⁻¹); and operating conditions (brine inlet temperature (30–68°C), air sweep velocity (0–6 m s⁻¹), and salt concentration in the feed brine (0–3 M)). A water flux of 0.8–3.3 kg m⁻² h⁻¹ was obtained using this type of hollow fiber with an inlet brine temperature of 25–65°C. It was found that, for our application, the optimal specifications for the ion-exchange hollow fibers were an outside diameter of 1.2 mm, a wall thickness of 0.1 mm, and an ion-charge density of about 1.0 meq g⁻¹. This information is required as basic data for the design of a prototype water desalination system based on a pervaporation system that uses this type of ion-exchange hollow fiber membrane.