Poly(ionic liquid)-derived nanoporous carbon analyzed by combination of gas physisorption and small-angle neutron scattering

The preparation of nanoporous carbon materials and their characterization combining small-angle neutron scattering (SANS) with gas physisorption is presented. Carbon with a porous structure and tunable form is obtained here by a salt-templating approach using poly(ionic liquid) as precursor. SANS in combination with contrast matching by deuterated p-xylene was used for a separation of the scattering component deriving from the density fluctuations of the carbon matrix and the inaccessible porosity. The resulting scattering curves could be used for an unambiguous characterization of the pore structure of the materials. SANS curves measured at different partial pressure of the matching agent p-xylene were used for a differential filling of the micro- and mesopores. The analysis using the chord length distribution (CLD) was employed to determine the specific surface area and the pore size at different adsorption steps. The SANS results were in good agreement with the quenched solid density functional theory (QSDFT) analysis of the nitrogen physisorption. By the comparison of both characterization methods the pore shape could be determined. The combination of both SANS and gas physisorption is thus shown to provide a comprehensive characterization of the pore structure of the carbon monoliths throughout the entire pertinent length scale.     

FRAGMENTATION IN RANDOM PORE STRUCTURES

The problem of fragmentation of solid phase in reacting porous structures that consist of d (d = 1,2,3) mutually perpendicular bundles of parallel, randomly overlapping cylindrical capillaries is considered. The evolution of fragmentation with the porosity is studied using a Monte Carlo stimulation procedure which rests in using the trajectories of test particles randomly travelling in the solid phase to identify fragments and determine fragment size and fragment surface area distributions. Our results show that fragmentation occurs at about the same value of pore number density per bundle for all d values. This observation is used to develop a correlation that satisfactorily predicts the extent of fragmentation in 2- and 3-bundle capillary structures using the simulation results for pore structures consisting of a single bundle of overlapping capillaries.     

固态Si颗粒在Na2O-CaO-SiO2多孔微晶玻璃中氧化的均匀性

加入固态Si颗粒为Na2O?CaO?SiO2(NCS)多孔微晶玻璃配合料的气泡成核质点以调控孔结构,研究了固态Si颗粒在NCS配合料形成熔体过程中的氧化行为,用ANSYS模型模拟了NCS多孔微晶玻璃配合料的热场分布. 结果表明,固态Si颗粒在NCS熔体形成过程中的氧化始于650℃,固态Si颗粒具有促进NCS配合料热场均匀分布的作用,且在NCS熔体形成过程中氧化程度相同,氧化过程不会影响NCS多孔微晶玻璃孔径分布的均匀性.     

Fabrication of Highly Porous Chromium Carbide with Multiple Pore Structure

A unique process, which consists of camphene‐based freeze‐casting and reactive sintering, has been developed to fabricate highly porous Cr₃C₂ ceramics, which were featured with a well‐defined multisize porous structure, consisting of large pore channels throughout the sample and small pores on the porous struts. The porous structure was found to be affected by the solid loading content and the casting temperature. Decreasing the solid loading content or increasing the freezing temperature increased the size of large pore channels. However, the size of small pore was not significantly influenced by the variation in the freeze‐casting parameters. Compared with other techniques reported for the fabrication of porous ceramics, high porosity can easily be achieved by this method. The sintering mechanism of the formation of the porous structure was also discussed in this study.     

Optimization of structure and properties of polyphenylene sulfide porous membrane by controlling the process of thermally induced phase separation

Polyphenylene sulfide (PPS) porous membranes were successfully prepared from miscible blends of PPS and polyethersulfone (PES) via thermally induced phase separation followed by subsequent extraction of the PES diluent. The morphologies, crystalline structures, mechanical properties, pore structures and permeate fluxes of the PPS porous membranes obtained from different phase separation processes were characterized and are discussed. During the phase separation in the heating process, PPS and PES mainly underwent liquid–liquid phase separation, and then a nonhomogeneous porous structure with a mean pore size of 100 μm and a honeycomb‐like internal structure formed on the membrane surface. The phase separation of PPS/PES occurring in the cooling process was easier to control and the related pore diameter distribution was more regular. In the process of direct annealing, as the phase separation temperature decreased, the pore size distribution became more homogeneous and the mean diameter of the pores also decreased gradually. When the phase separation temperature decreased to 200 °C, PPS membranes with a network structure and a uniform as well as well‐interconnected porous structure could be obtained. In addition, the maximum permeation flux reached 1718.03 L m^–2 h^–1 when the phase separation temperature was 230 °C. The most probable pore diameter was 6.665 nm, and the permeate flux of this membrane was 2.00 L m^–2 h^–1; its tensile strength was 17.07 MPa. Finally, these PPS porous membranes with controllable pore structure as well as size can be widely used in the chemical industry and energy field for liquid purification. © 2020 Society of Chemical Industry     

Study on the effect of micro geometric structure on heat conduction in porous media subjected to pulse laser

Based on fractal theory, different two-dimensional fractal structures were constructed to simulate the practical porous media. Effective thermal conductivity for porous media was calculated by means of the finite volume method. Theoretical analysis of thermal response in the porous media under various heating conditions was performed with a multi-layer hyperbolic heat conduction model with volumetric heat generation. The results obtained in this paper indicate that pore size and micro distribution have a far-reaching impact on the heat conduction in porous media. If we assumed that both the thermal conductivity and the heat capacity of the solid phase is larger than those of liquid phase, decreasing the pore size and porosity is helpful to enhance the heat transfer in porous media and the peak of temperature increases with pore size and porosity. With the same pore size and porosity, the effect of the pore micro-geometric distribution on heat conduction in porous media is obvious. The method presented in this paper may suggest a valuable approach to theoretically evaluate the effect of pore micro-geometric structure on heat conduction in porous media.     

水醇淀粉凝胶的形成及多孔淀粉的制备

以木薯淀粉为原料,水和乙醇为混合介质,利用溶胶-凝胶法及超临界CO₂干燥制备多孔淀粉,分别考察了水醇比、糊化时间、固含量、冷藏时间、乙醇置换用量、置换时间等对凝胶体积收缩率和质量损失率的影响,通过扫描电子显微镜、比表面积及孔径分布测试仪、X射线衍射仪表征了多孔淀粉形貌及孔结构,并考察了多孔淀粉的吸油性能。结果发现,水醇比为19∶1,固含量为13%,糊化时间为30min,冷藏时间为5天,醇置换量为5mL/g,置换时间为30min,水醇凝胶的体积收缩程度和质量损失相对较小,多孔淀粉的比表面积为122m²/g,平均孔径为25.6nm,大豆油的吸附率可达457%（质量比）。研究结果表明,适当调整固含量,能改善凝胶的三维网孔密度,增大多孔淀粉的比表面积及孔容;水醇淀粉凝胶中的淀粉分子能形成一定结晶结构的网络骨架,利于维持水醇凝胶的骨架稳定性。     

Accessibility of pores in coal to methane and carbon dioxide

Fluid–solid interactions in natural and engineered porous solids underlie a variety of technological processes, including geological storage of anthropogenic greenhouse gases, enhanced coal bed methane recovery, membrane separation, and heterogeneous catalysis. The size, distribution and interconnectivity of pores, the chemical and physical properties of the solid and fluid phases collectively dictate how fluid molecules migrate into and through the micro- and meso-porous media, adsorb and ultimately react with the solid surfaces. Due to the high penetration power and relatively short wavelength of neutrons, small-angle neutron scattering (SANS) as well as ultra small-angle scattering (USANS) techniques are ideally suited for assessing the phase behavior of confined fluids under pressure as well as for evaluating the total porosity in engineered and natural porous systems including coal. Here we demonstrate that SANS and USANS can be also used for determining the fraction of the pore volume that is actually accessible to fluids as a function of pore sizes and study the fraction of inaccessible pores as a function of pore size in three coals from the Illinois Basin (USA) and Bowen Basin (Australia). Experiments were performed at CO₂ and methane pressures up to 780 bar, including pressures corresponding to zero average contrast condition (ZAC), which is the pressure where no scattering from the accessible pores occurs. Scattering curves at the ZAC were compared with the scattering from same coals under vacuum and analysed using a newly developed approach that shows that the volume fraction of accessible pores in these coals varies between ～90% in the macropore region to ～30% in the mesopore region and the variation is distinctive for each of the examined coals. The developed methodology may be also applied for assessing the volume of accessible pores in other natural underground formations of interest for CO₂ sequestration, such as saline aquifers as well as for estimating closed porosity in engineered porous solids of technological importance.     

低场核磁法测定凝胶过滤介质的孔径分布

凝胶过滤介质在蛋白质、多糖等生物大分子的分离纯化过程中具有非常重要的作用,其中介质的孔径分布是决定分离纯化效果的关键因素。由于绝大部分凝胶过滤介质是软凝胶,因此很难用常规的方法如压汞法、低温氮吸附法等测定其孔径分布。本文探索了利用低场核磁共振测定凝胶过滤介质的孔径分布的方法。首先通过抽滤、自制琼脂糖凝胶块等实验确定了峰的归属,明确了介质孔内水、介质间隙水和自由水在核磁共振横向弛豫时间(T₂)图谱上的分布范围;随后与逆体积排阻层析法(ISEC)测定的结果相对比,得出层析介质孔径和介质孔内水弛豫时间的关系;最后通过高斯正态拟合得到了介质的孔径分布。实验结果证实了低场核磁共振法测定凝胶过滤介质孔径分布的可行性。该法操作简单、测定迅速,并可以为其他层析介质孔径分布的测定提供参考。     

多孔介质中三组分气体扩散的网络分析

采用有效介质理论和平滑域近似的方法 ,对乙烯、氩气和二氧化碳在γ -Al2 O3 内的三组分扩散进行了网络分析 ,同时又用定态扩散实验加以验证 .研究结果表明 ,在确定了多孔介质孔结构参数 (平均配位数 )和孔尺寸参数 (孔径分布 )的前提下 ,通过网络分析的方法就可以获得有关多孔介质中多组分气体扩散的信息 .从而 ,建立起了用多孔介质微观性质描述宏观扩散过程的基本方法     

Production of high porosity nanoparticles of cerium oxide in clay

Cerium oxide nanoparticles modified montmorillonite was obtained by interaction of a clay with (NH₄)₂Ce(NO₃)₆. The mean size of cerium oxide nanoparticles in clay was at 3.5 nm. The product was an amorphous solid and showed high permanent porosity and stability at high temperatures. The amorphous structure of the sample was proven by X-ray diffraction and electronic diffraction. The porous structure was studied by means of chemisorption and it was shown that samples calcined at 550 °C had S_BET = 239 m²/g; micropore volume = 0.1839 cm³/g; average pore diameter = 3.07 nm.     

Pore structure modification of silica matrix infiltrated with paraffin as phase change material

Temperature-controlling solid–liquid phase change material (PCM) infiltrated in a porous matrix is becoming attractive for aerospace applications. The properties of the pore structure are crucial factors in the selection of porous materials for PCM infiltration. The main purpose of this study is to adjust the pore structure of porous silica matrices with different molar ratios of ethanol (EtOH) and tetraethoxysilane (TEOS) for PCM infiltration. Five compositional ratios of EtOH/TEOS were introduced to prepare the silica with different pore size through sol–gel processing, and the pore structures were analyzed by N₂ adsorption–desorption measurements and scanning electron microscopy. Results indicate that the pore size increases with a larger value of the EtOH/TEOS molar ratio. Open cell pore structure and pore size of silica were observed and calculated. For EtOH/TEOS ratios of 10 and 20, the synthesized silica matrices had average pore sizes of 53.1 nm and 56.0 nm, respectively, exhibiting better infiltration. Moreover, the maximum mass fraction of paraffin as PCM in the silica matrices reached up to 75 wt%.     

Preparation of high strength lamellar porous calcium silicate ceramics by directional freeze casting

In this study, porous calcium silicate (CS) ceramics with oriented arrangement of lamellar macropore structure were prepared by directional freeze casting method. The lamellar macropores were connected by the micropores on the pore wall, which had good pore interconnectivity. The effects of solid loading of the slurry, freezing temperature, sintering additive content, and sintering temperature on the microstructures and compressive strength of the synthesized porous materials were investigated systematically. The results showed that with the increase of solid loading (≤20 vol%) and sintering additive content, the sizes of lamellar pores and pore walls increased gradually, the open porosity decreased and the compressive strength increased. The sintering temperature had little effect on the pore size of the ceramics, but increasing the sintering temperature (≤1050 °C) promoted the densification of the pore wall, reduced the porosity, and improved the strength. The decrease of freezing temperature had little effect on porosity, but it reduced the size of lamellar pore and pore wall, so as to improve the strength. Finally, porous CS ceramics with lamellar macropores of about 300–600 μm and 2–10 μm micropores on the pore wall were obtained. The porous CS ceramics had high pore interconnectivity, an open porosity of 66.25% and a compressive strength of 5.47 MPa, which was expected to be used in bone tissue engineering.     

氮吸附法表征多孔材料的孔结构

采用低温氮吸附法表征了具有不同孔结构的碳纳米管、碳分子筛、活性炭、分子筛和石墨化炭黑等多孔材料的孔径分布。氮吸附一脱附等温线利用康塔公司NOVA3000在相对压力0．001-1范围内测定。五种材料的比表面积在100-1000m2／g之间。低压下的吸附等温线和高压下的脱附等温线分别用HK方法和BJH方法解析,结果表明:五种多孔材料既含有发达的微孔,又含有一定数量的中孔。孔径大小及其分布的细微信息在色谱采样中能够预测吸附剂的吸附性能,也是新型多孔材料开发的关键。     

小角Ｘ射线散射模糊数据解析方法

小角Ｘ射线散射（ＳＡＸＳ）是研究多孔材料结构的一种有效方法，可得到孔径分布、平均孔径、比表面、界面层厚度、分形维数等许多微结构住处、ＳＡＸＳ理论公式基于点状光源（针孔准直），但实践中则大多采用长狭准直条件，简要综述了ＳＡＸＳ在长狭缝准直条件下直接应用模糊强度进行煤、炭、干凝胶、分子筛等多孔材料结构解析的方法，并与针孔准直进行了对比。     

Analyses of (AD)-sorption for the estimation of pore-network dimensions and structure

The interpretation of pore dimensions based on physical ad-desorption analyses is central to the characterization of pore network structure. Several approaches have been proposed and are commonly employed in the analysis of physical adsorption and/or desorption to deduce the dimensions of the porous network. These approaches assume either theoretical (e.g., BET, the Halsey equation as interpreted by Pierce et al., or the more recent analyses of microporosity) or standard isotherms as model(s) for the sequential calculations required in estimating the pore network dimensions. Subsequent representation of the pore dimensions and the relationship between these distributions in dimension and other experimental parameters (such as catalytic activity, adsorptivity or transport); thus, depend explicitly on the model employed in the analyses. Each instrument currently available for the measurement of porous solid structure by sorption employs the same specific models for the relationship between the volume ad-desorbed and the dimensions of the porous network that is being characterized.This paper analyzes the interpretation of porous dimensions based on the sequential calculations required in the analyses. A new approach is proposed which is based on a modification to current practices reflecting Halsey's original theory for the thickness of the adsorbed layer (as a function of P/P ₀). Further, the calculations of the incremental changes in the exposed surface area are discussed as they relate to pore network structure. A method is proposed to infer the differences in pore shape. Sorption data are analyzed by these new approaches, and these analyses will be compared with those approaches currently employed. Analyses based on these modified approaches provide a dramatically more consistent interpretation of the sorption data and the corresponding pore network structures.     

Effects of pore structure on thermal conductivity and strength of alumina porous ceramics using carbon black as pore-forming agent

In the present work, carbon black (CB) works as a pore-forming agent in the preparation of alumina porous ceramics. The pore structures (i.e. mean pore size, pore size distribution and various pores size proportions) were characterized by means of Micro-image Analysis and Process System (MIAPS) software and mercury intrusion porosimetry. Then their correlation and thermal conductivity as well as strength were determined using grey relation theory. The results showed that the porosity and mean pore size increased against the amount of CB, whereas the thermal conductivity, cold crushing strength and cold modulus of rupture reduced. The <2 μm pores were helpful for enhancing the strength and decreasing the thermal conductivity whereas the >14 μm pores had the opposite effects.     

Development of porous polymer monolith by photoinitiated polymerization

Porous polymer monoliths have been successfully prepared by photoinitiated polymerization of butyl methacrylate (BMA) and ethylene glycol dimethacrylate (EDMA) monomers in porogenic solvent of methanol. Mercury intrusion porosimetry and scanning electron microscope are used to characterize the porous properties; nevertheless, the pore size obtained from both techniques is not comparable. The porous structure of the porous polymers is controlled by the phase separation during the polymerization and crosslinking. By varying the composition of the starting solution such as initiator fraction, BMA/EDMA ratio, porogen fraction, and UV intensity, porous polymers with median pore size from about 140 nm to 3 μm can be obtained, and the pore size distribution for majority of the porous polymers is also narrow. The results present a very positive prospect to microfluidic applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Correlations between pore structure parameters and gas permeability of corundum porous materials

Corundum porous materials with different contents of calcium hexaluminate formed in situ were prepared using pure calcium aluminate cement as the calcium source. The surface fractal dimensions of the porous materials were calculated based on the experimental data of mercury intrusion. Correlations between pore structural parameters and the permeability coefficients k₁ and k₂ of the porous materials were then studied based on the grey system theory. The results showed that pores in the corundum porous materials have great fractal characteristics. The surface fractal dimension was a significant pore structural parameter that reflected the complexity of pore shape, pore surface, and pore-size distribution, which had the maximum correlation coefficient with the permeability of this type of porous materials. The apparent porosity and pore-size distribution had relatively high correlation coefficients to the permeability as well. Increasing the apparent porosity and the volume percentage of larger pores, and decreasing the volume percentage of smaller pores all benefited the permeability of the porous materials. In addition, the mean pore size and median pore size showed lower correlation coefficients to the permeability—especially for porous materials with a wide pore-size distribution.     

曲折因子与多孔介质微观结构的定性关系

采用三维网络模型对多孔介质中的两组分气体扩散过程进行了计算机模拟 .在考虑了多孔介质微观结构的前提下 ,分析了外界因素和多孔介质结构对曲折因子的影响 .结果表明 ,曲折因子仅与多孔介质的孔道连通性———网络配位数密切相关 ,而与孔道的几何尺寸、扩散温度、扩散物种及浓度无关 .经过Wicke -Kallenbach定态扩散实验验证了这一定性结论的可靠性 .