电子显微镜研究分子筛的新进展

电子显微镜在沸石分子筛的研究中起着重要的作用.阐述了透射电子显微镜(TEM)和扫描电子显微镜(SEM)技术研究沸石分子筛的原理,描述了使用不同种类的电子显微镜剖析沸石分子筛的形态、尺寸、粒径分布等,并介绍了近年来电镜技术对沸石分子筛,特别是对新型功能介孔材料及手性介孔材料的研究进展.电子显微镜的发展将推动分子筛及纳米材料在选择性催化/吸附过程中的应用.     

A new method to quantify parameters of membrane morphology from electron microscopy micrographs by texture recognition

A new method has been developed in order to automatically quantify parameters of membrane morphology from micrographs obtained through microscopy techniques. The parameters estimated by this algorithm are: pore size distribution, porosity, pore symmetry, regularity and tortuosity, as well as various statistical measures. These properties determine the performance of a membrane.The proposed method is based on texture recognition. It first identifies the pores present in the membrane from a cross-section micrograph of it, then labels them and finally makes the corresponding measurements. The main difference and advantage of this technique with respect to previous proposals is that the algorithm does not perform generic particle recognition, but direct scanning of typical pore structures and no user decisions are needed in all the steps of the process. Additionally, the proposed technique does not only determine typical parameters, such as pore size, but also particular characteristics of membrane topology, such as symmetry.The source information consists of cross-section membrane micrographs that can be typically obtained from electron microscopy (scanning or transmission), as well as from other types of microscopy, which are the most common acquisition techniques used by membranologists. The system provides quantitative, systematic and fast results, which represents a significant advance in the field of membrane analysis.     

Image-based characterization of cement pore structure using wood’s metal intrusion

Mercury intrusion porosimetry is a widely used technique for characterization of the pore size distribution of cement-based materials. However, the technique has several limitations, among which are the ink bottle effect and a cylindrical pore geometry assumption that lead to inaccurate pore size distribution curves. By substituting Wood’s metal for mercury as the intruding liquid, scanning electron microscopy and imaging techniques can be applied to the sample after intrusion. The molten Wood’s metal solidifies within the pore structure of the sample, which allows it to be sectioned and observed in the scanning electron microscopy. From here, the sample can be analyzed both qualitatively, by observing the changes in the appearance of the sample as the intrusion process progresses, and quantitatively, by applying image analysis techniques. This study provides insight for better interpretation of mercury intrusion porosimetry results and the possibility for quantitative characterization of the spatial geometry of pores in cement-based materials.     

Processing of porous ceramics: Piezoelectric materials

The paper reviews processing techniques used to produce porous ceramics with tri-dimensionally interconnected porosity, in a wide range of pore volumes and pore size and distribution. Attention is focused on the development of porous electroceramics and especially piezoelectric PZT materials. The porosity can be introduced through dry or wet techniques. In the dry techniques, a fugitive phase is added to the perovskitic powder by mechanical mixing. Wet techniques involve the manipulation of suspensions and a better control of the final morphology and microstructure of the samples can be achieved by the colloidal approach. The whole spectrum of techniques for generation of porosity is surveyed; it includes burnout of volatile particles or thermally unstable sponge structures, generation of porosity by foaming, slip casting, tape casting, direct consolidation, solid freeform fabrication, die pressing. Porosities of up to 70% are obtained in aerogels by sol–gel processing. The pore size distribution and microstructural differences resulting from various processing parameters influence the physical properties, particularly the acoustic/piezoelectric response of PZT materials.     

Pore size-controlled synthesis of 3D hierarchical porous carbon materials for lithium-ion batteries

3D hierarchical porous carbons (3DCs) with different pore size distributions are prepared by using Ni(OH)₂ as template. The morphology, crystalline features, pore structure and surface composition of the hierarchical porous carbons are characterized using various analytic techniques including scanning electron microscopy, transmission electron microscopy, N₂ physical adsorption, powder X-ray diffraction and X-ray photoelectron spectroscopy. It is found that the pore size distributions of the 3DCs play an important role in the lithium-storage capacity when they are used as anode materials for rechargeable lithium-ion batteries. The typical sample 3DC-20 has a specific reversible capacity of 630 mAh g^??1 in the first cycle and and 363 mAh g^??1 after 50 cycles. The high capacity of 3DC-20 can be attributed to the existence of the largest amount of micropores with 0.6–0.9 nm pore width, which increase the lithium storage capacity; in addition, the existence of mesoporous and macroporous effectively shortens the distance for charge diffusion, the turbostratic graphite structure low resistance for electron conduction.     

Macroporous mullite materials prepared by novel shaping strategies based on starch thermogelation for thermal insulation

A rigorous microstructural analysis of porous mullite materials developed using novel shaping strategies based on the starch consolidation casting, and their thermal properties in relation to the processing and starch type were accomplished in view of their use as thermal insulators. In order to characterize the size and morphology of pore, basic size and 2D shape factors, and global 3D stereological parameters were determined using microscopy techniques. Results indicated that the porosity volume, pore connectivity degree, and mean free path were the determining factors of the lowest heat transfer by conduction registered in materials prepared with cassava starch. This material is the best candidate to be used in thermal insulation.     

Structured carbon adsorbents from clay, zeolite and mesoporous aluminosilicate templates

Porous carbons templated from inorganic materials such as zeolites and mesoporous molecular sieves received considerable attention in the last decade. In this context, we discuss the effects of different templating structures on the carbons yielded. We describe templating using a commercial cationic clay (Wyoming bentonite), a commercial zeolite (Tosoh H-Beta) and a synthetic mesoporous aluminosilicate (Al-MCM-48), as exemplars of the categories of inorganic templates we have studied. The main carbon precursor used was furfuryl alcohol, complemented in some materials by an additional treatment using propylene carbon vapour deposition. The structures of the templates and carbons were compared using electron microscopy and powder X-ray diffraction. Carbons were further characterised with elemental analysis and nitrogen adsorption. The templating process is more complex than previously reported; the combination of these different techniques enhances the understanding of its mechanisms. A careful study of the synthesised carbons’ pore size distributions using DFT with various pore geometries was carried out and comparison with two commercial carbon adsorbents made, in order to assess the potential of such templated carbons for gas separation and gas storage.     

Porosity measurements in suspension plasma sprayed YSZ coatings using NMR cryoporometry and X-ray microscopy

A large variety of coatings are used to protect structural engineering materials from corrosion, wear, and erosion, and to provide thermal insulation. In this work, yttria-stabilized zirconia coatings produced by suspension plasma spraying were investigated with respect to their microstructure and especially their porosity, as the porosity affects the thermal insulation of the underlying component. To determine porosity, pore size distribution, and pore shape, the coatings were investigated using novel advanced characterization techniques like NMR cryoporometry and X-ray microscopy. In general, the porosity is inhomogeneously distributed and the coatings showed a large variety of pore sizes ranging from a few nanometers to micrometers.     

Thermoporometry as a new tool in analyzing mesoporous MCM-41 materials

Thermoporometry, a calorimetric procedure, is applied for measuring the pore size distribution, pore volume and surface area of mesoporous MCM-41 molecular sieves using water as the adsorbate. A series of MCM-41 materials with various pore diameters was synthesized and subjected to the new method. The results are compared with nitrogen physisorption. Both methods are complementary, whereby the former provides also information about the pore shape. MCM-41 materials with pores wider than 50 Å also allow the use of benzene as the adsorbate in thermoporometry.     

Morphological control of porous ethylene‐vinyl acetate copolymer membrane obtained from a co‐continuous ethylene‐vinyl acetate copolymer/poly(ϵ‐caprolactone) blend

Ethylene‐vinyl acetate copolymer (EVA)/poly(?‐caprolactone) (PCL) blend (50/50 w/w) with co‐continuous morphology was prepared via melt mixing for fabricating microporous EVA membrane materials through selective solvent extraction. Shear flow and quiescent annealing techniques were employed to control co‐continuous phase size in the EVA/PCL blend, and the time‐ and temperature‐dependent relations of phase size were then evaluated theoretically. Using these techniques, microporous EVA membrane materials with various pore sizes ranging from 2 µm to more than 200 µm were obtained. In contrast to the porous EVA membrane prepared by the traditional way of solvent casting/particulate leaching, the as‐obtained microporous membrane shows a higher level of interconnectivity and much narrower pore size distribution with uniform pore structure. © 2013 Society of Chemical Industry     

Effect of various pore formers on the microstructural development of tape-cast porous ceramics

Various types of pore formers have been used for the fabrication of ceramics with controlled porosity. This study addresses a detailed and systematic comparison of different pore formers (e.g. graphite, polymethyl methacrylate, sucrose and polystyrene) with distinct features such as size, distribution and morphology of particles and decomposition/oxidation behavior. Investigations also involve their effect on the rheological properties of the slurries and the microstructural development of laminated porous ceramic tapes.Morphological features of the pore former particles were characterized using laser diffraction, B.E.T. surface area measurement and scanning electron microscopy (SEM) techniques as their thermal decomposition/oxidation behavior were determined by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) methods. Tape compositions were developed and optimized in order to incorporate identical volumetric loadings of the materials in the tape formulations with different pore formers for a reliable comparison of their pore forming characteristics. Porous yttria stabilized zirconia (YSZ) ceramics were fabricated without macroscopic defects (e.g. cracks, warpage and delamination) by developing heating profiles based on the identified thermal properties of the pore formers. Characterization of the sintered porous ceramics by SEM and mercury intrusion porosimetry techniques revealed novel relationships between the physical properties of the utilized pore formers, processing parameters and final pore structures.     

Tuning mesoporous molecular sieve SBA-15 for the immobilization of α-amylase

The present work describes the immobilization of α-amylase over well ordered mesoporous molecular sieve SBA-15 with different pore diameters synthesized by post synthesis treatment (PST) hydrothermally after reaction at 40°C. The materials were characterized by N₂ adsorption–desorption studies, small angle X-ray diffraction, scanning electron microscopy and high resolution transmission electron microscopy. Since α-amylase obtained from Bacillus subtilis has dimensions of 35 × 40 × 70 Å it is expected that the protein have access to the pore of SBA-15 (PST-120°C) with diameter 74 Å. The pore dimension is appropriate to prevent considerable leaching. The rate of adsorption of the enzyme on silica of various pore sizes revealed the influence of morphology, pore diameter, pore volume and pH.     

Controlling the textural parameters of mesoporous carbon materials

The mesoporous carbon materials prepared by inorganic templating technique using mesoporous silica, SBA-15 as a template and sucrose as a carbon source, have been systematically investigated as a function of sucrose to mesoporous silica composition, with a special focus on controlling the mesoporous structure, surface morphology and the textural parameters such as specific surface area, specific pore volume and pore size distribution. All the materials have been unambiguously characterized by XRD, N₂ adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron microscopy, and Raman spectroscopy. It has been found that the porous structure, morphology and the textural parameters of the mesoporous carbons materials, CMK-3-x where x represent the sucrose to silica weight ratio, can be easily controlled by the simple adjustment of concentration of sucrose molecules. It has also been found that the specific surface area of the mesoporous carbon materials systematically increases with decreasing the sucrose to silica weight ratio. Moreover, the specific pore volume of the materials increases from 0.57 to 1.31 cm³/g with decreasing the sucrose to silica weight ratio from 5 to 1.25 and then decreases to 1.23 cm³/g for CMK-3-0.8. HRTEM and HR-FESEM also show a highly ordered pore structure and better surface morphology for CMK-3-1.25 as compared to other materials prepared in this study. Thus, it can be concluded that the sucrose to silica weight ratio of 1.25 is the best condition to prepare well ordered mesoporous carbon materials with good textural parameters, pore structure and narrow pore size distribution.     

A review on the micro- and nanoporous polymeric foams: Preparation and properties

A great number of studies on new synthetic materials have been focused on the preparation of different porous polymers. This review explains the principles and techniques of polymeric foam formation and their features followed by an overview of papers on polymeric porous materials. Physical blowing agent, phase separation, leaching, etching, and thermal decomposition are the main techniques for foam formation that are briefly described. This discussion covers different polymeric foams with various morphologies, pore sizes, and properties. These polymeric foams can be applied for various purposes, including tissue engineering, membranes in separation process, electrical and thermal insulators, packaging, and scaffolds.     

Quantitative Electron Microscopic Investigation of the Pore Structure in 10:90 Colloidal Silica/Potassium Silicate Sol-Gels

Transmission electron microscopy (TEM), scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), and nitrogen sorption technique (BET) were utilized to characterize the microstructure of a 10:90 wt% colloidal silica/potassium silicate gel as first described by Shoup. Gels in the unsintered state (15% theoretical density) were prepared for microscopy by the techniques of ultramicrotomy, Pt/C replication, and pore casting. Electron microscopic images of the ultramicrotomed thin sections (70 nm) show that the unfired gel possesses three distinct species of pores which are referred to as the micropores, mesopores, and macropores. The average micropore diameter was found to be 4 nm as determined by nitrogen desorption. Quantitative stereological analysis of the ultramicrotomed sections indicated that the average circular and lengthwise dimensions of the cylindrical mesopores were 0.15 and 0.39 μm, respectively. Similarly, this same analysis determined the average spherical macropore diameter to be 0.83 μm. In contrast, MIP results suggested that these gels possessed a unimodal pore size distribution centered around the 0.2-μm pore size. The discrepancy between MIP and microscopy can be explained by viewing the void space as a pore-throat network. Experimental evidence for this type of pore geometry was obtained from stereo pairs of Pt/C replicas and thick microtomed sections (0.5 μm) which gave information about particle connectivity and pore casts which depicted the pore connectivity in three dimensions.     

纳米孔阵列结构阳极氧化铝模板的应用研究现状

对铝基材实施阳极氧化处理,可在其表面形成氧化铝多孔膜。当氧化铝多孔膜的纳米孔排列成规则的阵列结构时,氧化铝多孔膜将具有许多其它纳米材料无法比拟的优势。综述了以具有规则纳米孔阵列结构的阳极氧化铝薄膜作为模板,通过复制、沉积、吸附等技术,制备具有各种特殊用途纳米材料的制备工艺,使用这些方法制备的纳米材料已经广泛地应用于催化、气体吸收、分离膜、微电子器件等。     

Influence of pore former on porosity and mechanical properties of Ce0.9Gd0.1O1.95 electrolytes for flue gas purification

Single layered porous Ce_0.9Gd_0.1O_1.95 electrolytes were fabricated by tape casting using different types, shapes and sizes of pore formers and their respective strength and stiffness were compared. The sintered bodies were characterized by scanning electron microscopy, mercury porosimetry, impulse excitation technique (Young modulus) and flexural strength measurements, to investigate the role of the different pore formers on the properties of the compounds. The compared techniques used to evaluate porosity give consistent results. The ratio between open and total porosities, evaluated from mercury porosimetry, varies depending on the used pore formers. The stiffness and strength of the compounds show an exponential dependency to the total porosity. By considering the open porosity instead (functional porosity), we observe that samples with platelets shaped pore formers have higher in-plane strength than spherical pore formers. An optimum can be found in term of Weibull strength and strain of samples obtained with the various pore formers by considering the dependency on the functional open porosity instead of the total porosity.     

Sorption of petroleum products by carbon sorbents

A comparative study of the adsorption of petroleum products by micro- and macroporous carbon sorbents was performed. For this purpose, four carbon sorbent samples prepared from various raw materials by various processing techniques were used. The pore structures and adsorption capacities of these sorbents for petroleum products were studied. It was found that the adsorption of petroleum products on porous and nonporous carbon sorbents occurred in different manners. In this case, macroporous sorbents with a weakly developed structure of sorbing micro- and mesopores exhibited a maximum capacity for petroleum products.     

Synthesis and characterization of LTA zeolite with uniform intracrystal mesopores directed by bridged polysilsesquioxane monomer

An ordered mesoporous LTA zeolites (MLTA) have been synthesized in presence of the bridged polysilsesquioxane monomer (BS-1) as mesoporogen. The relatively well-defined small-angle X-ray diffraction peaks and nitrogen sorption isotherms with narrow pore size distribution centered at around 2.2 nm both indicated the presence of uniformly mesopores in MLTA samples. The scanning electron microscopy and transmission electron microscopy observations further confirmed that the uniform and partially interconnected intracrystal mesopores were randomly distributed throughout the globular particles with rugged surfaces. Interestingly, removal of the BS-1 resulted in uniform mesopore diameters that are nearly consistent with the molecular size of BS-1 (1.8 nm). ²⁹Si MAS NMR revealed that the BS-1 was linked to MLTA zeolite crystal surface through 2 Si–O bonds and 3 Si–O bonds before calcinations. Nitrogen sorption analysis showed that the mesoporosity in MLTA samples could be adjusted by adding different amounts of BS-1 in starting gels. Relative to conventional mesoporous materials, one obvious feature of MLTA is that the resultant mesopores were structured by the bridged polysilsesquioxane monomer instead of commercial polymers or micelles, which broad the routes in synthesizing of various mesoporous materials with controllable pore size distribution, adjustable mesopore volume, and large surface area.     

Suppression of gold nanoparticle agglomeration and its separation via nylon membranes

Use of ultraporous nylon membrane is one of the most widely employed techniques for removal of hard and soft nanoparticles in the semiconductor industry,and the accurate determination of membrane pore size is necessary in order to avoid manufacturing defects caused by contamination.The gold nanoparticle has several benefits for the evaluation of polymeric membranes;however,the nanoparticles agglomerate easily on the nylon membrane and make it difficult to evaluate the membrane precisely.The properties of 2-amino-2-hydroxymethyl-1,3-propanediol (ADP) ligand in gold nanoparticle solution were systematically investigated,and ADP was utilized for improved evaluation of the nylon membranes.Nylon membrane used in this study was prepared by phase inversion techniques.Ultrathin dense layer on top of the membrane surface and Darcy structures in the microporous membrane support were observed.The gold particle rejection was carried out at various pH values from 4 to 14 and higher rejection was observed at pH 4 and 8.The suppression of gold colloid agglomeration using ADP and monodispersity of gold colloids was also analyzed by confocal laser scanning microscopy (CLSM),transmission electron microscopy (TEM),and scanning electron microscopy (SEM).van der Waals interaction energy of the particles was reduced in the addition of ADP.The presence ofADP ligand in the gold solutions prevented the agglomeration of gold nanoparticles and reduced the adsorption of the particles on the nylon membrane surface,leading to precise evaluation of membrane pore sizes.