Porous SiC Ceramics Derived from Tailored Wood-Based Fiberboards

Specific modification of properties such as porosity and pore size of engineered wood-based source material enables the custom design of porous wood-derived SiC that is produced by carbothermal reduction between the carbonized wood-based material and an infiltrated silica sol. In contrast to bulk wood, the anisotropic shrinkage of the source material is less distinctive and can be controlled. Furthermore, the obtained structural properties of the material are isotropic. Material processing and properties of the wood-derived ceramic material are described in this paper.     

Intermediate Temperature Internal Oxidation of a SiC/SiCN Composite with a Polymer‐Derived Matrix

SiC‐based composites exhibit oxidative embrittlement at intermediate temperatures. Although the mechanisms of internal oxidation in composites with initially hermetic matrices have been studied extensively, comparable studies on composites with semipermeable matrices, such as those produced by polymer infiltration and pyrolysis, have not been reported. The present article focuses on the latter class of composites, specifically a SiC_f /SiCN_m with a dual BN/Si₃N₄ fiber coating. It describes detailed SEM and TEM analyses of the microstructure before and after oxidation in dry air or water vapor at 800°C. The results show that internal oxidation is more aggressive in water vapor and occurs appreciably even in the absence of an applied stress. The sequence of oxidation of the constituent phases appears to be consistent with the underlying thermodynamic hierarchy for the respective oxidation reactions. Notably, contrary to existing models based on preferential oxidation of BN coatings, oxidation occurs first on the SiC fiber surfaces and the Si₃N₄ overcoat; crystalline BN remains even after significant fiber and matrix oxidation has occurred. The results are discussed in terms of rate‐controlling kinetic processes, the effect of oxidant type, and applied stress.     

Processing of Porous SiC by Aluminum‐Derived Binders and Sacrificial Porogen Leaching Method

Porous SiC was successfully fabricated by a facile and energy efficient sacrificial porogen leaching method using in situ synthesized aluminum‐based binders by reaction bonding at low sintering temperatures of 600–1000°C. Porous SiC ceramics with porosity in the range of 30–58% and compressive strength of 1–33 MPa were obtained. Interconnected bimodal pores were produced by both stacking of SiC particles and leach out of salt. During sintering, the aluminum binder experienced metal to ceramic transformations forming various alumina polymorphs (γ, δ, θ and α‐Al₂O₃). The porogen content and sintering temperatures significantly influence the properties of porous SiC.     

基于Mn-MOF的多孔碳/MnO复合材料的制备及催化性能研究

首先通过溶剂法制备甲酸锰(Mn-MOF)晶体,接着以Mn-MOF为前驱体,在惰性条件下制备了结构、形貌可控的多孔碳/MnO复合物。采用XRD、BET和SEM表征Mn-MOF前驱体和多孔碳/MnO复合物的结构、形貌等。结果表明,600℃下获得的多孔碳/MnO复合物含有立方相MnO和无定型多孔碳。将多孔碳/MnO复合物用于催化臭氧分解,催化效率可达92.3%,重复利用性好。     

Preparation of Porous Polymethyl Methacrylate/Organo-Montmorillonite Composite Membranes for Phenolic Compound Adsorption

The preparation of porous poly(methyl methacrylate)/organo-montmorillonite composite membranes for adsorption application was carried out via entrapment methods. The sponge-like membrane structure was characterized by a scanning electron microscope, whereas the X-ray diffraction, Fourier transform infrared, and thermogravimetric analyses confirmed the incorporation of organo-clays inside the composite membranes. To investigate the applicability of the composite membranes on phenolic compound adsorption, batch-mode adsorption of p-nitrophenol at 0.025 mg/mL was conducted. The optimum feed organo-clay/polymer ratio was 0.3 for the membrane prepared by the emulsion polymerization method, and in this case 75% of p-nitrophenol was adsorbed after 34 h. 80% methanol was selected as the desorbent for its high ability to desorb p-nitrophenol from the composite membrane. The membrane performance in the flow process was similar to the batch result, and the adsorption/desorption cycle was successfully repeated three times.     

莫来石/SiC复相多孔陶瓷的制备及性能研究

用高岭土、Al2O3粉和SiC粉末为原料,活性碳为造孔剂制备莫来石/SiC多孔陶瓷.测定了试样的显气孔率、气孔孔径分布和抗弯强度,并分别用XRD和SEM分析晶相组成和断面显微结构.结果表明:莫来石的理论设计质量的分数小于10%时,莫来石/SiC多孔陶瓷的显气孔率随其设计量的增多而急剧降低;莫来石理论设计量继续增加时,试样显气孔率缓慢降低并趋于稳定.气孔孔径随莫来石设计量的增加而急剧减小.抗弯强度随莫来石设计量的增加而先增大,在莫来石理论设计量为20%时达到最大值,此后逐渐降低.SEM分析结果表明:与其他试样相比,莫来石设计量为40%的试样中存在较多的多孔"微区".     

Fabrication and Characterization of Near‐Net‐Shape In Situ Reaction‐Bonded Porous Cordierite/SiC Ceramics

Porous cordierite/SiC ceramics were fabricated by in situ reaction bonding using α‐SiC, α‐Al₂O_3, and MgO powders as the starting materials. During sintering, part SiC is oxidized to SiO₂ and then the latter reacts with Al₂O₃ and MgO to form cordierite. As a result, porous cordierite/SiC ceramics were obtained, and the ceramics are strengthened by the residual SiC. Due to the large volume expansion introduced by the oxidation of SiC, the ceramics exhibit small sintering‐induced dimension variations. In addition, a fine‐grained microstructure and good thermal and mechanical properties were obtained for the porous cordierite/SiC ceramics.     

SiC/莫来石复相多孔陶瓷气孔率和强度的影响因素

以煅烧高岭土、Al(OH)3粉末、SiC粉末为主要原料,以石墨为造孔剂制备了SiC/莫来石复相多孔陶瓷,研究了造孔剂含量、碳化硅颗粒粒径以及烧结温度对SiC/莫来石复相多孔陶瓷抗弯强度和气孔率的影响,并分别用XRD和SEM分析晶相组成和断面显微结构.结果表明:当SiC粒径为60 μm,造孔剂含量为15％时,在1400℃下保温3h制备的样品综合性能最佳,其孔隙率为30.3％,抗折强度达到58.0 MPa.     

Porous Si/SiC Composite Based on Nonwoven Cellulosic Fabrics: Synthesis and Characterization

The microstructure and properties of porous Si/silicon carbide (SiC) composites manufactured from nonwoven cellulosic fabrics have been investigated. A fibrillar reaction product with a microstructure reproducing the initial preform morphology consisting of β-SiC and unreacted Si was obtained. Improvement of strength is expected to be achieved by increase of SiC content and reduction of porosity.     

Fabrication and Characterization of Electrospun Dopants/PS Composite Fibers with Porous and Hollow‐Porous Structures

Three different dopants are used to fabricate electrospun dopants/polystyrene (dopants/PS) composite fibers from PS solution and PS sol. The relative humidity and the influence of the dopants on the morphologies, diameter, porous structures, and dopant distribution of electrospun PS fibers are investigated. Compared to those obtained from PS solution, electrospun dopants/PS composite fibers from PS sol with hollow‐porous and multichannel hollow‐porous structures present significant advantages due to the multi‐stage degree of interfacial structure and diversity of the internal environment. In comparison to coaxial electrospun PS fibers, the electrospun dopants/PS composite fibers from PS sol obtained in one step have an improved yield and a simplified technological process simultaneously, leading to significant competitiveness in fields such as catalysis, fluidics gas storage, and sensing.

     

Planar,Polysilazane‐Derived Porous Ceramic Supports for Membrane and Catalysis Applications

Porous, silicon carbonitride‐based ceramic support structures for potential membrane and catalysis applications were generated from a preceramic polysilazane precursor in combination with spherical, ultrahigh‐molecular weight polyethylene microparticles through a sacrificial filler approach. A screening evaluation was used for the determination of the impact of both porogen content and porogen size on pore structure, strength, and permeability characteristics of planar specimens. By optimizing both the composition as well as cross‐linking parameters, maximum characteristic biaxial flexural strengths of 65 MPa and porosities of 42% were achieved. The evolution of an interconnected, open‐pore network during thermal porogen removal and conversion of the preceramic polymer led to air permeabilities in the order of 10^?14 m². The materials were further exposed to long‐term heat treatments to demonstrate the stability of properties after 100 h at 800°C in oxidizing, inert, and reducing environments. The determined performance, in combination with the versatile preparation method, illustrates the feasibility of this processing approach for the generation of porous ceramic support structures for applications at elevated temperatures in a variety of fields, including membrane and catalysis science.     

Polymer‐Derived SiC/B4C/C Nanocomposites: Structural Evolution and Crystallization Behavior

Structural evolution and crystallization behavior between 600°C and 1450°C during the preparation of bulk SiC/B₄C/C nanocomposites by the pyrolysis of CB‐PSA preceramic were investigated. The CB‐PSA preceramic converts into carbon‐rich Si–B–C ceramics up to 800°C. Structural evolution and crystallization of Si–B–C materials could be controlled by adjusting the pyrolytic temperature. The Si–B–C ceramics are amorphous between 800°C and 1000°C. Phase separation and crystallization begin at 1100°C. The crystallization of β‐SiC takes place at 1100°C and B₄C nanocrystallites generate at 1300°C. The sizes of β‐SiC and B₄C nanocrystals increase with the pyrolytic temperature rising. In addition, the boron‐doping effect on structural evolution was studied by comparing the crystallization and graphitization behavior of Si–B–C ceramics and the corresponding Si–C materials. Boron is helpful for the growth of β‐SiC nanocrystals and the graphitization, but harmful for the nucleation of β‐SiC crystallites.     

Porous Carbon Spheres Derived from Hemicelluloses for Supercapacitor Application

With the increasing demand for dissolving pulp, large quantities of hemicelluloses were generated and abandoned. These hemicelluloses are very promising biomass resources for preparing carbon spheres. However, the pore structures of the carbon spheres obtained from biomass are usually poor, which extensively limits their utilization. Herein, the carbon microspheres derived from hemicelluloses were prepared using hydrothermal carbonization and further activated with different activators (KOH, K₂CO₃, Na₂CO₃, and ZnCl₂) to improve their electrochemical performance as supercapacitors. After activation, the specific surface areas of these carbon spheres were improved significantly, which were in the order of ZnCl₂ > K₂CO₃ > KOH > Na₂CO₃. The carbon spheres with high surface area of 2025 m²/g and remarkable pore volume of 1.07 cm³/g were achieved, as the carbon spheres were activated by ZnCl₂. The supercapacitor electrode fabricated from the ZnCl₂-activated carbon spheres demonstrated high specific capacitance of 218 F/g at 0.2 A/g in 6 M KOH in a three-electrode system. A symmetric supercapacitor was assembled in 2 M Li₂SO₄ electrolyte, and the carbon spheres activated by ZnCl₂ showed excellent electrochemical performance with high specific capacitance (137 F/g at 0.5 A/g), energy densities (15.4 Wh/kg), and good cyclic stability (95% capacitance retention over 2000 cycles).     

多孔SiC陶瓷/石蜡复合相变材料定型封装及热性能研究

以微米级SiC粉为原料,采用冷冻干燥工艺制备具有连贯层状孔结构的SiC陶瓷。以多孔SiC陶瓷为基体,石蜡为相变芯材,通过真空浸渍法制备多孔SiC陶瓷/石蜡复合相变材料,研究了石蜡在层状多孔SiC陶瓷内的浸渗行为及复合材料的储热性能。结果表明,层片状多孔SiC陶瓷的显微形貌对石蜡的浸渗过程及储热性能有明显影响。当石蜡负载量为21.7%(质量分数)时,复合相变材料熔融温度为59.6 ℃,凝固温度为53.9 ℃,相变潜热为28.4 J/g,室温下的热导率为2.4 W·(m·K)^-1。复合相变材料吸热峰和放热峰强度随着石蜡负载量减少而降低,当温度为200 ℃时,多孔SiC陶瓷/石蜡复合相变材料失重为5%(质量分数),表明材料具有良好的热稳定性。复合相变材料在100 ℃热处理30 min后陶瓷基体未发生形变,经100次热循环后具有稳定的相变潜热和良好的定型能力。     

氟化铝添加量对碳化硅/莫来石复合多孔陶瓷性能的影响

本文以碳化硅(SiC)、气相SiO2、纳米Al2O3和AlF3·H2O为原料,制备出了碳化硅/莫来石复合多孔陶瓷,主要研究了AlFa·H2O添加量、烧结温度对多孔陶瓷抗弯强度、气孔率、孔径分布等性能的影响.用SEM、XRD研究了多孔陶瓷的微观形貌和物相组成.结果表明:AlF3·H2O对莫来石的生成有明显的促进作用,1300℃时,添加AlF3·H2O的样品中检测到莫来石相,多孔陶瓷气孔率随AlF3·H2O加入量增加而升高,而抗弯强度随其增高而先增加后减小,AlF3·H2O添加量为4wt％时,多孔陶瓷气孔率为42.8％,抗弯强度为31.1 MPa.     

Preparation of C/C‐SiC Composites from All‐Cellulose Precursors

All‐cellulose composites (ACCs) are manufactured from high‐performance cellulose fibers and a cellulose‐containing ionic liquid (IL) as matrix‐forming dope via wet‐winding processes, using different concentrations of cellulose in the IL. ACCs are carbonized at 1650 °C and then infiltrated with liquid silicon. Application of a carbonization aid (ammonium dihydrogenphosphate, ADHP) substantially improves the carbon yield after carbonization but also results in the depletion of the mechanical properties of the final carbon/carbon silicon carbide (C/C‐SiC) material. The microstructure of the porous carbon/carbon preforms strongly depends on both the concentration of cellulose in the IL and the concentration of ADHP. A C/C‐SiC composite manufactured from 6 wt% cellulose in the matrix‐forming dope, in the absence of ADHP, has a maximum flexural strength of 60 MPa. New C/C‐SiC composites with different shapes including Z‐profiles and tubes are successfully manufactured from pre‐shaped ACC precursors. These composites keep their shape during carbonization and the final siliconization process step.     

不同铝源对SiC/堇青石复相多孔陶瓷的制备及性能影响

以碳化硅、氮化铝、层析氧化铝、氢氧化铝、氟化铝、滑石为主要原料,石墨为造孔剂通过原位反应烧结技术制备碳化硅/堇青石复相多孔陶瓷.研究了含铝化合物种类、烧结温度、石墨含量对SiC/堇青石复相多孔陶瓷相组成、微观结构、气孔率和抗折强度的影响,同时对S0组在1200℃烧结温度下制得的SiC/堇青石复合多孔陶瓷的孔径分布进行了测试分析.结果表明:以AlN为铝源在1200℃下烧结,石墨含量在15％时,堇青石结合SiC多孔陶瓷的抗弯强度和气孔率两项综合性能达到最优,气孔率为31.99％,相应的弯曲强度86.20 MPa.S0组的平均孔径大小在3.0191 μm.     

Synthesis and Application of an Organotin Functionalised Highly Porous Emulsion‐Derived Foam

A new type of organotin chloride catalyst supported on a highly porous polymer has been prepared by polymerisation of a highly concentrated reverse emulsion the organic phase of which contains several monomers. This polymer‐supported organotin chloride shows a good activity and good stability towards dehalogenation and radical cyclisation.     

Porous Ni/ZrO2 Cermet from Highly Concentrated Composite Colloid

Rheology and shaping of concentrated cermet suspensions consisting of nickel (Ni) and yttria‐stabilized zirconia (YSZ) nanoparticles in water have been examined over a broad range of volumetric solids concentration (? = 0.1–0.4) and Ni fraction (f_Ni = 0.15–0.45). Preferential adsorption of pyrogallol‐poly(ethylene glycol) polymer (i.e., Gallol‐PEG) on surface of the Ni and YSZ particles imparts steric hindrance between the suspending particles so that fluidity can be obtained under shear stress. The cermet suspensions exhibit shear‐thinning flow behavior under steady‐shear measurement over shear rates of 10⁰–10³ s^?1. Yield stress and yield strain of the suspensions appear to vary pronouncedly with ? and f_Ni under oscillatory shear over a shear‐strain range of 10^?1–10³%. With the Gallol‐PEG adsorption, an apparent viscosity less than 6 × 10^?1 Pa.s at a shear rate of 10² s^?1 has been obtained for the highly concentrated composite suspension with ? of 0.40 and f_Ni of 0.25. A high solids concentration effectively prohibits phase segregation during wet‐shaping processes. Uniform green compacts have been obtained from slip casting of the concentrated cermet mixture (? = 0.30) without use of binder and are then fired at 1200°C under reducing atmosphere to form porous Ni/YSZ compacts. Relative sintered density increases from 65% to 75% of the theoretical value when f_Ni was increased from 0.15 to 0.45, due mainly to the lower sintering temperature required for the Ni phase.     

Pressure‐less joining of C/SiC and SiC/SiC by a MoSi2/Si composite

A MoSi₂/Si composite obtained in situ by reaction of silicon and molybdenum at 1450°C in Ar flow is proposed as pressure‐less joining material for C/SiC and SiC/SiC composites. A new “Mo‐wrap” technique was developed to form the joining material and to control silicon infiltration in porous composites. MoSi₂/Si composite joining material infiltration inside coated and uncoated C/SiC and SiC/SiC composites, as well as its microstructure and interfacial reactions were studied. Preliminary mechanical strength of joints was tested at room temperature and after aging at service temperatures, resulting in interlaminar failure of the composites in most cases.