多孔氮化硅陶瓷透波材料研究进展

多孔氮化硅陶瓷透波材料具有优异的机械性能、耐热性能及介电性能,成为透波材料科学研究领域中的热点之一。本文介绍了多孔氮化硅陶瓷的主要制备技术,并对国内外多孔氮化硅陶瓷透波材料的应用研究进展进行了综述。     

多孔氮化硅陶瓷制备及其性能研究进展

多孔氮化硅(Si_3N_4)陶瓷由于具有优异的力学性能、良好的抗热震和低介电常数等特点,在极端力/热环境下具有很大的应用潜力。研究表明:不同的制备工艺对多孔氮化硅陶瓷晶粒尺寸、微结构有很大影响,从而影响材料的力学性能;介电性能受气孔率、相组成影响;渗透率受气孔率、气孔尺寸、弯曲度的影响。综述了多孔Si_3N_4陶瓷的烧结工艺、成型工艺及其相关性能研究,并结合目前的研究热点,指出了未来多孔氮化硅陶瓷研究的发展方向。     

多孔石英基体上CVD法沉积氮化硅涂层的工艺、结构与性能研究

以甲硅烷(20％甲硅烷+80％氢气)和氨气作为反应前驱体,选择孔隙率为20％左右的多孔石英陶瓷基体,采用CVD法在多孔石英基体表面制备了氮化硅涂层.研究了沉积反应温度、反应压力、反应气体配比以及沉积时间等工艺参数对附着力的影响,确定了CVD法制备氮化硅涂层的最佳工艺参数,通过对所得涂层及复合材料进行抗弯强度和介电性能的表征,探讨了氮化硅涂层对多孔石英基体力学性能和介电性能的影响.     

常压烧结制备多孔氮化硅陶瓷研究

选用Al2O3、Y2O3、Lu2O3三种氧化物作为烧结助剂,采用凝胶注模成型和气氛保护常压烧结工艺,成功制备了具有高强度和高气孔率的多孔氮化硅陶瓷材料.本文研究了三种烧结助剂对多孔氮化硅的力学性能、介电性能和微观结构的影响,以及对氮化硅陶瓷的烧结促进作用,结果表明Y2O3具有最佳的烧结活性促进作用,其微观结构表明β-Si3N4棒状晶粒搭接结构是使多孔氮化硅陶瓷材料具有较好力学性能的重要原因.     

烧结助剂对多孔氮化硅陶瓷的力学性能及介电性能的影响

通过添加烧结助剂,采用常压烧结工艺制备出不同气孔率(19%～54%)的氮化硅陶瓷.采用Archimedes法、三点弯曲法和Vickers硬度测试法测量了材料的密度、气孔率、抗弯强度及硬度.用X射线衍射及扫描电镜检测了相组成和显微结构.用谐振腔法测试了氮化硅陶瓷在10.2 GHz的介电特性.结果表明:材料具有优良的介电性能.随着烧结助剂的减少,样品中气孔率增加,力学性能有所下降,介电常数和介电损耗降低.添加Lu2O3所制备的氮化硅陶瓷的力学性能和介电性能优于添加Eu2O3或Y2O3制备的氮化硅陶瓷.当气孔率高于50%时,多孔氮化硅陶瓷(添加入5%的Y2O3或Lu2O3,或Eu2O3,质量分数)的抗弯强度可达170 MPa,介电常数为3.0～3.2,介电损耗为0.000 6～0.002.     

多孔氮化硅陶瓷作为罩体材料的应用研究

多孔氮化硅陶瓷由于其良好的弯曲强度、介电性能在航天航空领域得到了广泛应用。本文对多孔氮化硅陶瓷作为罩体材料的应用进行研究,对其作为防热承力材料进行温度场计算及试验研究,通过仿真及试验研究得出,多孔氮化硅陶瓷作为罩体材料耐热温度达到1400℃,热结构匹配及抗热震性能良好,能够满足某高速飞行器的使用要求。     

无机复合涂层对多孔氮化硅性能影响的研究

利用溶胶-凝胶法制备在多孔氮化硅的表面制备了无机复相陶瓷涂层,利用扫描电镜、红外光谱等手段研究了涂层的形貌和结构,并采用三点弯曲法研究了材料的力学性能,讨论了涂层前后基体的性能变化,结果表明:涂层对基体的抗弯有明显的提高,最大提高20%;用涂层封孔后后,材料的气孔率和吸水率明显下降,对多孔氮化硅介电性能影响很小。     

氮化硅多孔陶瓷制备国内专利技术综述

多孔氮化硅陶瓷材料因其能够充分发挥氮化硅陶瓷和多孔陶瓷两者的优异性能,广泛应用于机械、化工、海洋工程、航空航天等重要领域。制备孔隙率和孔隙结构可控、高强度、低介电常数的氮化硅多孔陶瓷是实现其应用的关键。本文在检索了大量国内专利文献的基础上,对氮化硅多孔陶瓷制备技术信息进行统计和分析,并对其未来技术发展进行了预测。     

多孔氮化硅微观组织结构对力学性能的影响

通过添加造孔剂苯甲酸,利用气氛压力烧结技术制备出了不同气孔率(40%～70%)的多孔氮化硅陶瓷,研究了显微结构对材料力学性能的影响;通过分析发现发育较好的长柱状β-氮化硅晶粒保证了材料获得良好的室温力学性能;而材料密度低、晶粒发育不完全是多孔氮化硅陶瓷力学性能下降的主要原因。本文制备的多孔氮化硅断裂形式为沿晶和穿晶断裂模式,当陶瓷气孔率为52%时,弯曲强度为195MPa。     

多孔氮化硅陶瓷的研究进展

综述了多孔氮化硅陶瓷材料的国内外研究现状和进展,介绍了多孔氮化硅陶瓷的主要制备方法,分析了微观组织对多孔氮化硅陶瓷力学性能的影响,并与其他多孔陶瓷进行了性能比较,最后展望了多孔氮化硅陶瓷的发展前景.     

Porous polymers prepared via high internal phase emulsion polymerization for reversible CO2 capture

A series of porous polymers with different pore volumes, pore sizes, and crosslinking densities were synthesized by high internal phase emulsion (HIPE) polymerization. The crosslinked polymerized HIPEs (polyHIPEs) were formed by the copolymerization of 4-vinylbenzyl chloride and divinylbenzene using water droplets in conventional or Pickering HIPEs as the templates. These porous materials were further modified by quaternization and ion exchange to introduce quaternary ammonium hydroxide groups. The resulting polyHIPEs were utilized as sorbents for reversible CO₂ capture from air using the humidity swing. The effect of pore structure on the CO₂ adsorption and desorption processes was studied. The polyHIPEs containing large pores and interconnected porous structures showed improved swing sizes and faster adsorption/desorption kinetics of CO₂ compared to a commercial Excellion membrane with similar functional groups.     

Porous ceramics with tri-modal pores prepared by foaming and starch consolidation

Porous silica ceramics with tri-modal pores were prepared, based on the generation of foams from silica/starch composite slurry and the subsequent stabilization of the structure by starch consolidation. The rheology of the original slurry and the foamed one were evaluated and compared. After drying, the green bodies were debindered and sintered at 1250 °C for 5 h. The resulting materials consisted of a hierarchical structure with large-sized cells, moderate-sized pores in cell wall and small-sized voids among silica grains. The compressive strength of the sintered samples varied within the range of 4–17 MPa, corresponding to relative densities of 18–30%.     

Porous Co3O4 nanoplatelets by self-supported formation as electrode material for lithium-ion batteries

In this paper, we have reported a simple and rapid approach for the large-scale synthesis of β-Co(OH)₂ nanoplatelets via the microwave hydrothermal process using potassium hydroxide as mineralizer at 140 °C for 3 h. Calcining the β-Co(OH)₂ nanoplatelets at 350 °C for 2 h, porous Co₃O₄ nanoplatelets with a 3D quasi-single-crystal framework were obtained. The process of converting the β-Co(OH)₂ nanoplatelets into the Co₃O₄ nanoplatelets is a self-supported topotactic transformation, which is easily controlled by varying the calcining temperature. The textural characteristics of Co₃O₄ products have strong positive effects on their electrochemical properties as electrode materials in lithium-ion batteries. The obtained porous Co₃O₄ nanoplatelets exhibit a low initial irreversible loss (18.1%), ultrahigh capacity, and excellent cyclability. For example, a reversible capacity of 900 mAh g⁻¹ can be maintained after 100 cycles.     

Fabrication of Porous TiO<Subscript>2</Subscript> Hollow Spheres and Their Application in Gas Sensing

In this work, porous TiO₂ hollow spheres with an average diameter of 100 nm and shell thickness of 20 nm were synthesized by a facile hydrothermal method with NH₄HCO₃ as the structure-directing agent, and the formation mechanism for this porous hollow structure was proved to be the Ostwald ripening process by tracking the morphology of the products at different reaction stages. The product was characterized by SEM, TEM, XRD and BET analyses, and the results show that the as-synthesized products are anatase phase with a high surface area up to 132.5 m²/g. Gas-sensing investigation reveals that the product possesses sensitive response to methanal gas at 200°C due to its high surface area.     

CO Oxidation Over a Fine Porous Gold Catalyst Fabricated by Selective Leaching from an Ordered AuCu3 Intermetallic Compound

A fine porous gold catalyst has been fabricated by selective leaching of Cu from an ordered AuCu₃ intermetallic compound with 50%HNO₃ aqueous solution at 50 °C. This catalyst exhibited comparable areal rate (mol min⁻¹ m⁻²-cat) with the Au/TiO₂ catalyst for CO oxidation. The present study demonstrates that high catalytic activity of gold is originated neither from the presence of fine dispersed Au particles nor from Au-support perimeter interface.     

Porous alumina ceramics with highly aligned pores by heat-treating extruded alumina/camphene body at temperature near its solidification point

This study reports a novel way of increasing the pore size of highly aligned porous alumina ceramics by heat-treating an extruded alumina/camphene body at a temperature near its solidification point. The pore size obtained increased remarkably from 51 ± 8 to 125 ± 27 μm with increasing heat-treatment time from 1 to 24 h, due to the continuative overgrowth of the camphene dendrites during heat-treatment, while a highly aligned porous structure was preserved. In addition, interestingly, this heat-treatment enabled alumina walls to be densified quite well, whereas porous walls were observed in the sample produced without heat-treatment, which led to a considerable increase in compressive strength. The sample produced with a heat-treatment time of 12 h showed a high compressive strength of 11.6 ± 1.2 MPa at a porosity of approximately 84 vol%, which was much higher than that (0.28 ± 0.1 MPa) of the sample produced without heat-treatment.     

Porous Ceramic Membranes: Preparation, Transport Properties and Applications

The preparation and characterization of porous ceramic membranes is presented. These membranes consist of a macroporous support system, with or without a mesoporous intermediate layer, and a microporous top layer. For the macroporous support membranes two manufacturing routes are described: a conventional and a RBAO (Reaction Bonded Aluminium Oxide) route. The mesoporous -Al₂O₃ layer is obtained by means of a sol-gel dipcoating technique. Three microporous top layers are considered: SiO₂, Al₂O₃-pillared montmorillonite and Laponite. These top layers have different pore structures which results in different gas transport properties. A SiO₂ membrane can be used for H₂ removal from a gas mixture. Al₂O₃-pillared montmorillonite and Laponite membranes do not show specific gas separation properties. Dehydration of water/2-propanol mixtures by means of pervaporation also proved a different behavior for these microporous membranes.     

Near-Field Electron Energy Loss Spectroscopy in Porous Silicon

First results of an Electron Energy Loss Spectroscopy in the Near Field (NFEELS) mode of n⁺ porous silicon are described here. Sequences of EELS spectra in the low loss energy range (0–30 eV) were recorded, using a scanning transmission electron microscope, as the e-beam was scanned across a nano-hole surrounded by Si platelets. This technique is shown to be very sensitive to spectral and spatial changes in the electromagnetic field distribution outside the surface of nanoparticles, governed by their local nature and shape.     

Preparation and Characterization of Porous SiO2-Al2O3-ZrO2 Prepared by the Sol-Gel Process

An experimental strategy was developed to obtain Si—Al—Zr transparent sols via the sol-gel process. The sol was prepared from Al(OBu^s)₃ (OBu^s: C₂H₅CH(CH₃)O), Zr(OPrⁿ)₄ (OPrⁿ: OCH₂CH₂CH₃) and Si(OEt)₄. The chelating agents acetylacetone (2, 4 pentanedione, acacH), and itaconic anhydride (2-methylenesuccinic anhydride, anhH) were employed separately to stabilize Al and Zr precursors in order to control their chemical reactivity, avoiding precipitation. In all cases a prehydrolyzed tetraethyl orthosilicate (TEOS) sol was the Si source. We use the Partial Charge Model as a theoretical indication of the stabilization of the Al and Zr species derived from the reaction with anhH and acacH. The sols were polymerized at room temperature (293 K) to obtain gels and these were dried and calcined at 673, 773 and 873 K in air. The characterization techniques were Small Angle X-ray Scattering (SAXS), Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Thermal Gravimetric (TGA) and Differential Thermal Analyses (DTA). The porosity and surface area of solids calcined at 673, 773 and 873 K were determined by N₂ adsorption/desorption isotherms. The corresponding average pore diameter was evaluated using the methods BJH, HK and DA. These models were used because all together cover the full range of the pore size.     

工艺参数对石英质多孔材料孔性能的影响

以长江沿岸低品位石英砂为主要原料,采用真空烧结制备了石英质多孔材料。通过实验分析发现:随烧结温度的升高、水料比的增大或发泡剂含量的增加,多孔材料的气孔率增大,抗压强度降低;而随着保温时间的延长,多孔材料的气孔率降低,抗压强度升高。通过优化得出最佳配比为:石英砂60 wt%、高岭土30 wt%、助烧剂9.6 wt%、发泡剂0.4 wt%。按这一最佳配比配料,在水料比为0.9的条件下球磨2 h制浆发泡,而后在1175°C烧结1 h,可以制备得到性能较佳的石英质多孔材料。