A combined top-down and bottom-up approach to fabricate silica films with bimodal porosity

We report a method to fabricate silica films with bimodal porosity based on the surfactant-directed self-assembly process followed by post-treatment with reactive ion etching (RIE). By RIE of a surfactant-templated mesoporous silica film with a 3D hexagonal structure, vertically-etched pores with the size of several tens of nanometers and the depth of ca. 60 nm are generated, while the original caged mesopores (ca. 5 nm in size) are still retained in the unetched parts of the film. Pre-treatment of the mesoporous silica film by wet-etching to expose the pores on the surface, followed by sputter deposition of a Pt layer for partial masking, is crucial for the anisotropic etching of the film. Such a combined top-down and bottom up approach offers an opportunity to fabricate silica films with hierarchical pore architectures.     

Computer simulation of effects of the pore size distribution on the kinetics of pressure-assisted final-stage densification

Most theoretical treatments of pressure-assisted densification of porous solids assume a single size for all pores. We remove this assumption and consider a distribution of pore sizes. Dissolution of intragranular pores by volume diffusion and dissolution of intergranular pores by grain-boundary diffusion are both treated. The evolution with time of pore size distributions is calculated for distributions that are initially described by log-normal and Weibull functions, and differences in predicted behaviours are discussed. The pore size distribution is then related to two important quantities: porosity and number of pores per unit volume. The assumption of a distribution of pore sizes is found to avoid certain unrealistic predictions obtained from models with a single pore size, such as abrupt disappearance of all pores and rapid approach to full density.     

Modeling of gas porosity and microstructure formation during dendritic and eutectic solidification of ternary Al-Si-Mg alloys

A two-dimensional(2-D)multi-component and multi-phase cellular automaton(CA)model coupled with the Calphad method and finite difference method(FDM)is proposed to simulate the gas pore for-mation and microstructures in solidification process of hypoeutectic Al-Si-Mg alloys.In this model,the pore growth,and dendritic and eutectic solidification are simulated using a CA technique.To achieve the equilibrium among multiple phases during ternary Al-based alloy solidification,the phase transition thermodynamics and kinetics are evaluated by adopting the Calphad method.The diffusion equations of hydrogen and two solutes are solved by FDM.The developed CA-FDM coupled model can be used for sim-ulating the evolution of gas microporosity and microstructures,involving dendrites and irregular binary and ternary eutectics,of ternary hypoeutectic Al-Si-Mg alloys.It has the capability of reproducing the interactions between the hydrogen microporosity formation and the growth of dendrites and eutectics,the competitive growth among the growing gas pores of different sizes,together with the time-evolving concentration fields of hydrogen and solutes.The simulated morphology of gas pore and microstructure has a good agreement with the experimental observation.The influences of the initial hydrogen concen-tration and cooling rate on the microporosity formation are investigated.It is found that the main portion of porosity formation occurs in the eutectic solidification stage through analyzing the profiles of porosity percentage and solid fraction varying with solidification time.The varying features of simulated porosity percentage,the maximum and average pores radii indicate that increasing initial hydrogen concentration promotes the formation of higher final porosity percentage and larger pores,while the size of gas pores will significantly reduce with increasing cooling rate,leading to a lower final porosity percentage.     

The influence of silica on pore diameter and distribution in PLA scaffolds produced using supercritical CO<Subscript>2</Subscript>

Macroporous polylactide (PLA) scaffolds were fabricated using a supercritical CO₂ foaming process. The addition of silica particles to the polymer matrix resulted in a significant modification in the pore size distribution exhibited by the scaffold. In the absence of silica, the scaffolds contained pores between 88 μm and 980 μm in diameter as determined using X-ray computed microtomography. The addition of silica at only 2 wt% resulted in the elimination of pores of >620 μm, with no significant influence on the total porosity of the material. This effect was attributed to the silica nucleating the formation of gas bubbles in the polymeric material. Although the addition of further silica to the scaffold resulted in a further reduction in modal pore diameter, when more than 20 wt% was added to the matrix little additional effect was noted. In addition to enabling some control over pore diameter, mineral deposition was shown to occur considerably more rapidly on the silica-modified scaffolds than on those containing no silica.     

A model for the porosity dependence of Young's modulus in brittle solids based on crack opening displacement

A crack opening displacement concept has been introduced to model the porosity dependence of Young's modulus in polycrystalline and single phase solids. In developing the theoretical model, it is assumed that each cylindrical cavity possesses radial cracks and spherical pores possess annular flaws. When an external stress is applied on such a solid, its elastic response is shown to be governed by the pore size, the width of an annular flaw, the number of pores (or pore volume fraction) and the flaw to pore size ratio. The validity of the present approach is tested against a number of experimental data.[/p]     

Three-dimensional visualization and quantification of microporosity in aluminum castings by X-ray micro-computed tomography

Porosity is a major issue in solidification processing of metallic materials.In this work,wedge die casting experiments were designed to investigate the effect of cooling rate on microporosity in an aluminum alloy A356.Microstructure information including dendrites and porosity were measured and observed by optical microscopy and X-ray micro-computed tomography(XMCT).The effects of cooling rate on secondary dendrite arm spacing(SDAS)and porosity were discussed.The relationship between SDAS and cooling rate was established and validated using a mathematical model.Three-dimensional(3-D)porosity information,including porosity percentage,pore volume,and pore number,was determined by XMCT.With the cooling rate decreasing from a lower to a higher position of the wedge die,the observed pore number decreases,the porosity percentage increases,and the equivalent pore radius increases.Sphericity of the pores was discussed as an empirical criterion to distinguish the types of porosity.For different cooling rates,the larger the equivalent pore radius is,the lower the sphericity of the pores.This research suggests that XMCT is a useful tool to provide critical 3-D porosity information for integrated computational materials engineering(ICME)design and process optimization of solidification products.     

Synthesis and characterization of silica aerogels by a novel fast ambient pressure drying process

Using cheap waterglass as silica source, silica aerogels were synthesized via a novel fast ambient drying by using an ethanol/trimethylchlorosilane (TMCS)/Heptane solution for modification of the wet gel. One-step solvent exchange and surface modification were simultaneously progressed by immersing the hydrogel in EtOH/TMCS/Heptane solution, in which TMCS reacting with pore water and Si–OH group on the surface of the gel, with ethanol and heptane helping to decrease the rate of TMCS reacting with pore water and extrude water from gel pores. The synthesized silica aerogel was a light and crack-free solid, with the density of 0.128–0.136 g/cm³ and 93.8–94.2% porosity. The microstructure, morphology and properties of the aerogels were studied by FTIR, SEM, TEM and BET measurement. The results indicate that silica aerogels exhibit a sponge structure with uniform nano-particle and pores size distribution. The specific surface areas of silica aerogels are 559–618 m²/g. And there is an obvious Si–CH₃ group on the surface of the silica aerogel.     

反应烧结多孔碳化硅的高温氧化行为

研究了反应烧结多孔碳化硅(RPSC)陶瓷在1200--1500℃干燥氧气中的氧化行为。 结果表明, 与碳化硅致密块的高温氧化行为不同, 温度越高, RPSC的氧化增重越小; RPSC的整个氧化过程分为氧化初期的快速增重阶段和缓慢氧化的平台阶段, 氧化动力学曲线符合渐近线规律。 RPSC的高温氧化在外表面和孔隙内同时发生, 孔隙内的氧化占主导地位, 最大氧化增重与孔隙率成线性关系。当孔内氧化速率高于氧气向孔内的传输速率时, 氧化主要发生在孔口附近, 氧化硅很快将孔封闭, 阻止了孔内继续氧化。     

Porous ceramic bone scaffolds for vascularized bone tissue regeneration

Hydroxyapatite scaffolds with a multi modal porosity designed for use in tissue engineering of vascularized bone graft substitutes were prepared by three dimensional printing. Depending on the ratio of coarse (mean particle size 50 microm) to fine powder (mean particle size 4 microm) in the powder granulate and the sintering temperature total porosity was varied from 30% to 64%. While macroscopic pore channels with a diameter of 1 mm were created by CAD design, porosity structure in the sintered solid phase was governed by the granulate structure of the printing powder. Scaffolds sintered at 1,250 degrees C were characterized by a bimodal pore structure with intragranular pores of 0.3-0.4 microm and intergranular pores of 20 microm whereas scaffolds sintered at 1,400 degrees C exhibit a monomodal porosity with a maximum of pore size distribution at 10-20 microm. For in-vivo testing, matrices were implanted subcutaneously in four male Lewis rats. Scaffolds with 50% porosity and an average pore size of approximately 18 microm were successfully transferred to rats and vascularized within 4 weeks.     

Nanospace engineering of KOH activated carbon

This paper demonstrates that nanospace engineering of KOH activated carbon is possible by controlling the degree of carbon consumption and metallic potassium intercalation into the carbon lattice during the activation process. High specific surface areas, porosities, sub-nanometer (<1 nm) and supra-nanometer (1-5 nm) pore volumes are quantitatively controlled by a combination of KOH concentration and activation temperature. The process typically leads to a bimodal pore size distribution, with a large, approximately constant number of sub-nanometer pores and a variable number of supra-nanometer pores. We show how to control the number of supra-nanometer pores in a manner not achieved previously by chemical activation. The chemical mechanism underlying this control is studied by following the evolution of elemental composition, specific surface area, porosity, and pore size distribution during KOH activation and preceding H(3)PO(4) activation. The oxygen, nitrogen, and hydrogen contents decrease during successive activation steps, creating a nanoporous carbon network with a porosity and surface area controllable for various applications, including gas storage. The formation of tunable sub-nanometer and supra-nanometer pores is validated by sub-critical nitrogen adsorption. Surface functional groups of KOH activated carbon are studied by microscopic infrared spectroscopy.     

Formation of porosity in ferritic ODS alloys on high temperature exposure

In order to investigate the formation, distribution, growth behavior and volume fraction of porosity at high temperatures in ferritic Oxide Dispersion Strengthened (ODS) superalloys MA 956, ODM 751 and PM 2000 were exposed at 1100 and 1200C in air and in 2% oxygen containing nitrogen atmospheres for up to 8760 h. All samples exhibited small amounts of porosity (% < 0.1) in the as-received condition. During the early stages of exposure (up to 10 h) pores were generally located close to the surface of the samples. Later they were found in the central region of the samples and the volume fraction of porosity and the mean pore size increased. After exposure for 240–1000 h, mainly depending on sample thickness, the size and volume fraction of porosity reached a maximum value and then decreased. SEM and EDS analysis results showed that some pores contained small amounts of Ti, Al and Y rich particles which were distributed over the internal surface of pores. It was noted that when the volume fraction of porosity and the size of pores began to decrease the pores had filled with the matrix material. A relation was established between the production environment of the materials and the growth behavior of the pores.     

Role of porosity in controlling the mechanical and impact behaviours of cement-based materials

This work deals with the influence of porosity on the tensile, the compressive and the impact behaviours of two fine cementitious mortars—one with silica fume and one without. The addition of silica fume is shown to change the pore size distribution. The mix without silica fume is characterized by porosity at the scale of the grains of fine sand (approximately 100 μm), while silica fume addition results in a more porous matrix with pore sizes of millimetre-length size. The mortar with silica fume shows a higher quasi-static compressive and flexural strength whereas the mix without silica fume is observed to be less compressible (by irreversible reduction of volume) under heavy confinement pressure (quasi-oedometric tests) and shows better ballistic performance. A numerical simulation of the impact tests employing the Krieg, Swenson and Taylor model, which accounts for both deviatoric and volumetric inelastic behaviour of the material, was undertaken using the data from quasi-oedometric tests. These calculations follow the experimental results and confirm the influence of the macroscopic porosity on the impact performance of cement-based materials.     

Fabrication of polymeric scaffolds with a controlled distribution of pores

The design of tissue engineering scaffolds must take into account many factors including successful vascularisation and the growth of cells. Research has looked at refining scaffold architecture to promote more directed growth of tissues through well-defined anisotropy in the pore structure. In many cases it is also desirable to incorporate therapeutic ingredients, such as growth factors, into the scaffold so that their release occurs as the scaffold degrades. Therefore, scaffold fabrication techniques must be found to precisely control, not only the overall porosity of scaffolds, but also the pore size, shape and spatial distribution. This work describes the use of a regularly shaped porogen, sugar spheres, to manufacture polymeric scaffolds. Results show that pre-assembling the spheres created scaffolds with a constant porosity of 60%, but with varying pores sizes from 200–800 μm, leading to a variation in the surface area and likely degradation rate of the scaffolds. Employing different polymer impregnation techniques tailored the number of pores present with a diameter of less than 100 μm to suit different functions, and altering the packing structure of the sugar spheres created scaffolds with novel layered porosity. Replacing sugar spheres with sugar strands formed scaffolds with pores aligned in one direction.     

Characterizing pore structure of cement blend pastes using water vapor sorption analysis

Pore structure is an essential factor that influences the mechanical behavior and durability of cement-based porous materials with or without added binders. An empirical model for water vapor sorption isotherms was employed to evaluate the pore structure of hardened cement pastes incorporating granulated blast furnace slag and silica fume. The model is an extension of the Brunauer–Emmett–Teller multilayer adsorption theory. Assuming cylindrical-shaped pores and an adsorbed liquid-like layer between the pore surface and gas phase, pore size distributions of the blended cement pastes were estimated. Calculated pore size distribution curves were compared with those measured by mercury intrusion porosimetry. Added granulated blast furnace slag and silica fume had minor effects on the monolayer adsorption capacity, but reduced the energy of the first and subsequent adsorption layers. The adsorbed liquid-like layer generated sharper pore size distribution peaks that were shifted to the mesoporous region. The pore size distributions were comparable with those determined by the mercury extrusion branch, but differed from those obtained by the mercury intrusion branch. Hysteresis of the water vapor adsorption–desorption isotherms and mercury intrusion–extrusion curves was due to the entrapment of a non-wetting phase in the porous system, further promoted by residual mercury in the pores following mercury extrusion.     

颗粒尺寸对SiC_P预制体孔洞三维特征的影响

通过模压成型和高温烧结制备了不同SiC_P颗粒尺寸(20、50、100和150μm)的预制体,采用高分辨率(~1.0μm)三维X射线断层扫描和三维孔隙网络结构模型,研究了SiC_P颗粒尺寸对预制体孔洞三维特征的影响。结果表明:随着SiC_P颗粒尺寸的增大,淀粉的间隙膨胀作用逐渐减弱,而颗粒堆积间隙逐渐增大。当SiC_P颗粒尺寸由20μm增大到100μm时,截面孔洞形貌更加平齐,面孔隙率均值减小,孔洞体积的空间分布均匀性和连通性都变差,孔洞和喉道的平均尺寸增大,而小尺寸孔喉数量减少,平均孔洞配位数减小;当颗粒尺寸继续增大至150μm时,间隙被更多较小尺寸颗粒填充,且颗粒表面残留网状粘结剂,都大大降低了孔洞体积的空间分布均匀性和连通性,使小尺寸孔喉数量增多,平均孔洞配位数增大。     

Combined kinetic and X-ray electron probe microanalysis characterization of local porosity variation and pore shape across anodic alumina films

Porous anodic alumina films on Al were prepared by anodic oxidation of Al in H₂SO₄ electrolyte at a constant temperature and current density and different thicknesses, up to ≈ 41 μm. Their cross section was examined by EPMA for revealing the variation of local porosity across the films and shape of pores while a kinetic model for film growth was developed describing the variation of pore diameter. It was found that the pores open, and local porosity increases, towards the film surface, predicting a conical pore shape, while the results coincided with those obtained by kinetic study. The EPMA analysis combined with kinetic results emerges as a promising tool for studying structural features of these films.     

From pore size distribution to an equivalent pore size of cement mortar

An experimental and theoretical study has been performed with the aim of quantifying pore size distribution curves and correlating them with water and oxygen permeability. Twenty mortars have been investigated which contained Portland cement, blast-furnace slag cement and silica fume as a binder. Admixtures have been used as well. The water-cement ratio varied between 0.4 and 0.75 and two curing conditions were applied. By the use of mercury intrusion porosimetry, the pore size distribution was determined. Water and oxygen permeability have been measured in the steady state. Equivalent pore sizes have been calculated which quantify the pore size distribution by a single number. This number is not a constant but depends on the physical transport mechanism. It is shown that equivalent pore size and porosity together are sufficient to predict the physical properties with an acceptable accuracy.     

Frost resistance and pore size distribution in bricks

Correlation between frost resistance, porosity and pore size distribution was examined. Different test methods were used to evaluate the frost resistance. Porosity and pore size distribution were examined in mercury intrusion porosimeter (MIP). Scanning electron microscopy gave a visual view of the pore geometry, pore size and porosity. A linear correlation was found between frost resistance and the inverse value of the intruded pore volume. A linear correlation was also found between frost resistance and percentage of pores with diameter bigger than 3 μm. The test results were analysed using statistical methods. From the MIP-test a frost resistance number can be calculated which indicates the frost resistance of the brick.     

Comparison of observed and simulated cement microstructure using spatial correlation functions

The microstructure of cement pastes, as revealed by SEM-BSE image analysis, was compared with a simulated structure generated by the University of Twente version of the CEMHYD3D hydration simulation model. The spatial array of unhydrated cement particles was simulated by the model. However, spatial features in capillary pore structure obtained by the simulation are different from the observed microstructure. This disagreement in the spatial structure is to be expected since there are fundamental differences in porosity as represented by the two methods. Only coarse pores are detected in the SEM examination while the total capillary porosity and its whole spatial distribution are virtually simulated in the model. A subset of the visible pores must be different in spatial statistics from the universal set of total porosity. Care must therefore be taken in interpreting agreement between simulation output and microscopically observed microstructure in images.     

A study of ultrafine porosity in hydrated cements using small angle neutron scattering

Small angle neutron scattering makes use of the neutron contrast due to differences in the scattering power between small, particulate regions and the general background medium, and has only very recently been applied to study the porosity in hydrated cement systems. The technique is applied to pore sizes below approximately 30 nm and produces data on pore size distribution, pore volume and pore shape without recourse to drying techniques and the potential structural degradation which may occur. Results indicate a bi-modal pore size distribution at approximately 5 and 10 nm diameter, with a total volume accounting for some several percent of the total cement block. The best estimate of the 5 nm pore shape is considered to be curved-faced tetrahedra. The pores appear to be relatively unaffected by changes in the water-to-cement ratio or accelerating admixture investigated, but macro defect free cement does show significant pore structure alteration.