Fabrication of porous magnesium spinel with directional pores by unidirectional solidification

A porous magnesium spinel (MgAl₂O₄) with directional pores was fabricated by unidirectional solidification in pressurized argon and hydrogen mixed gases. Two different kinds of pores with large directional and small facet shape were formed in the solidified samples. The former pores were dominant in the porous structure. A small amount of free corundum phase was formed in the solidified porous spinel as a secondary phase by vaporization of MgO component during the solidification process. With increasing total gas pressure, the pore size of the solidified samples decreased while no change in the porosity. The porosity and pore size of the samples increased with increasing hydrogen partial pressure. The porosities of the samples fabricated under 10%H₂–90%Ar and 1%H₂–99%Ar mixed gases were 30 and 10%, respectively, and that under Ar atmosphere was very low, non-porous.     

Mechanical and dielectric properties of porous magnesium aluminate (MgAl2O4) spinel ceramics fabricated by direct foaming-gelcasting

Porous ceramic materials have been broadly applied in various fields due to their multifunctional properties. Optimization of their microstructural characteristics, such as pore morphology, total porosity, and pore size distribution, which determine various properties of the final products, is crucial to improve their performances and thus extend their applications. In this study, single-phase porous MgAl₂O₄ materials were fabricated by direct foaming–gelcasting. With an increase in the foam volume from 260 to 350 mL, the total porosity and pore size of the porous ceramic increased, and its microstructure varied from mostly closed cells to open cells containing interconnected large pores (40–155 μm) and small circular windows (10–40 μm) in the ceramic skeleton. The total porosity could be tailored from 84.91% to 76.08% by modulating the sintering temperature and foam volume and the corresponding compressive strengths were in the range of 2.8–15.0 MPa. The compressive strength exhibited a power-law relationship with the relative density with indices of approximately 3.409 and 3.439, respectively. Porous MgAl₂O₄ ceramics exhibited low dielectric constants in the range of 1.618–1.910 at room temperature, which are well matched with theoretical calculations on account of a modified Bruggeman model. The porous MgAl₂O₄ ceramics with good mechanical and dielectric properties controlled easily by various sintering temperatures and foam volumes are promising for practical applications.     

Effects of pore shape and porosity on the properties of porous PZT 95/5 ceramics

Porous lead zirconate titanate (PZT 95/5) ferroelectric ceramics were prepared by sintering compacts consisting of PZT and pore formers. The piezoelectric, dielectric and ferroelectric properties of porous PZT ceramics were investigated as a function of pore shape and porosity. Piezoelectric coefficient (d₃₃), dielectric constant (ɛ₃₃) and remnant polarization (P_r) decreased with an increase in porosity, and the porous PZT ceramics with spherical pores exhibited better properties than that with irregular pores. Furthermore, the electrical conductivities of PZT ceramics were investigated to explain the phenomena that porous PZT ceramics exhibited lower dielectric loss (tan δ) than dense PZT ceramics in the temperature range from 250 to 500 °C.     

Surface and pore structure of deoiled acid-and heat-treated spent bleaching clays

Samples of spent bleaching clay were deoiled by hexane, methanol, hexane-methanol, and supercritical CO₂ extractions. The deoiled clays were regenerated by acid and heat treatments. Nitrogen adsorption isotherms for these samples are type IV with hysteresis loops corresponding to type H3, indicating slit-shaped pores. Used deoiled and dried samples have smaller surface areas and pore volumes than unused clay. The surface areas and pore volumes increased after heat treatment. Acidified heat-treated deoiled samples have smaller surface areas and greater pore volumes than unused clay, except for the methanol-deoiled sample. Thus, heat and acid treatments removed substances adsorbed in the pores that were not removed by solvents or CO₂ extraction. This was confirmed from the ratios of the cumulative surface area/BET surface area, as well as analysis of the pore size distributions, which indicated an increase in mesopores with radii of between 25 and 100 Å. The t-plots showed that smaller pores with sizes between 7 and 25 Å, present originally in the unused clays, were closed by heat treatment. These pores were absent in the deoiled and the heat-treated samples except for the heat-treated sample that was deoiled by hexane followed by methanol. Smaller pores, accompanied by an increase in surface area, were also observed for all deoiled samples after acid and heat treatments.     

Effect of closed pores on dielectric properties of 0.8Na0.5Bi0.5TiO3-0.2K0.5Bi0.5TiO3 porous ceramics

Porous 0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃ ceramics are fabricated via the pore-forming agent method with polymethyl methacrylate (PMMA) and stearic acid (SA) as pore forming agents, and microstructure observations demonstrate that the porosity, pore shape, and pore sizes can be controlled by the synthesis technology. The dielectric properties of porous ceramics are found not only correlated to the pore-matrix composite model, but also have a significant grain-size effect. Based on the Zener Theory, pining forces exerted by pores on the grain boundary are calculated, to explain the shape effect of pores on grain boundary migration. A phase-field simulation is carried out to investigate pore shape effect on the grain size regulation in porous polycrystalline, and simulation results are in good agreements with experiential results as well as theoretical calculations. Thus, a modified equation is proposed to predict the effective permittivity of the porous piezoelectric ceramics by considering effects of porosity, pore shape and grain size.     

Study on the mechanical properties of porous tin oxide

Despite the importance of tin oxide (SnO₂) in diverse functional applications, little information is available on the mechanical properties of bulk or porous SnO₂. In this study, porous SnO₂ was synthesized using an ice-templating method to produce a “dual” pore structure that comprises large wall pores (on the order of several micrometers) with small micropores (~2 µm) on their surfaces. The Vickers hardness decreased with increasing porosity and increased with increasing contiguity of struts. The compressive stress–strain curves of porous SnO₂ samples with porosity ranging from 48% to 73% were compared with both the Gibson–Ashby and the cellular-lattice-structure-in-square-orientation models, which generally represent the “lower” and “upper” bounds of yield strength for porous materials, respectively. As expected, the yield strength of the porous SnO₂ samples decreased with increasing porosity, and all the yield-strength values of porous SnO₂ fell between the two extreme prediction models. The sample with the lowest porosity of 48% exhibited sharply increasing elastic behavior followed by sudden rupture, as generally reported for bulk ceramics; however, the other samples with higher porosities ranging from 50% to 73% exhibited “porous-metal-like” behavior at strains of 15% or greater as a result of the fracturing of the solid walls between the pores.     

Formation of porous PLGA scaffolds by a combining method of thermally induced phase separation and porogen leaching

A novel method for the fabrication of porous poly(L -lactide-co-glycolide) (PLGA) scaffolds by combining thermally induced phase separation and porogen leaching is presented in this article. Big pores with about 75–400 μm diameters in the obtained scaffolds were generated by the porogen, sucrose particles, while small pores with diameters less than 20 μm induced via phase separation. Extraction of the solvent, chloroform by ethanol at cool temperatures could reduce the scaffold toxicity. Effects of PLGA concentration, freezing temperature, volume fraction of porogen, and introduction of β-tricalcium phosphate (β-TCP) on morphology, porosity, and compressive properties of the scaffolds were systematically discussed. Results showed that the size of small pores decreased by decreasing the polymer concentration and reducing the freezing temperature, whereas the interconnectivity of the scaffolds was improved by increasing the porogen fraction. The compressive modulus and strength were significantly lowered by increasing the scaffold porosity, that is, by increasing porogen fraction, or decreasing the polymer concentration, or reducing the freezing temperature. Addition of β-TCP into the scaffolds did not influence the compressive modulus significantly but tended to decrease the compressive strength. The obtained scaffolds with diverse pore sizes would be potentially used in bone tissue engineering. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

制备工艺对多孔Si_3N_4陶瓷介电性能的影响(英文)

采用添加成孔剂和冰冻-干燥法制备具有不同气孔率(30%～60%)的多孔Si3N4陶瓷,研究了不同制备工艺对多孔Si3N4陶瓷介电性能的影响.结果表明:不同的成型工艺制备出具有不同孔分布的氮化硅多孔陶瓷,添加成孔剂制备的多孔陶瓷具有较大的孔,洞分布在致密的基体上:冰冻-干燥法制备的多孔陶瓷具有复合孔分布.对样品的介电特性的研究表明,随着样品的气孔率增加,其介电常数和介电损耗减小;添加成孔剂制各样品的介电常数小于冰冻-干燥法制备样品,而其介电损耗较大,多孔Si3N4陶瓷的介电常数和介电损耗分别在5.21～2.91和9.6×10-3～2.92×10-3范围内变化.     

Imprinting of nanopores in organosilicate dielectric thin films with hyperbranched ketalized polyglycidol

Hyperbranched polyglycidol (PG) was synthesized via a new polymerization pathway of glycidol using zinc glutarate (ZnGA) as a catalyst. ZnGA was found to be a highly active catalyst for the ring-opening polymerization of glycidol. The complex chemical structures of hyperbranched PG and its ketalized derivative (K-PG) were determined by specialized ¹³C nuclear magnetic resonance spectroscopic techniques. In addition, a new soluble silsesquioxane copolymer, poly(methylsilsequioxane-co-1,4-bis(ethylsilsesquioxane)benzene), i.e. a PMSSQ-BESSQB precursor, was synthesized via the sol-gel reaction of its monomers. The precursor solution was found to produce good quality thin films. K-PG was found to have good solubility in common solvents and good miscibility with the PMSSQ-BESSQB precursor. Moreover, K-PG was found to exhibit a sacrificial thermal decomposition characteristic that makes it suitable for use as a porogen in the fabrication of porous PMSSQ-BESSQB dielectric films. K-PG can be loaded into the PMSSQ-BESSQB precursor at concentrations up to 40 wt%. Synchrotron grazing incident small-angle X-ray scattering studies of the porous thin films prepared from PMSSQ-BESSQB/K-PG composite films with various compositions found that the average size of pores in the porous dielectric films varies from 6.7 to 18.5 nm as the initial loading of the K-PG porogen is increased from 10 to 40 wt%. These pores are spherical and have a sharp interface with the dielectric matrix. The porosities P of the porous PMSSQ-BESSQB films were found to increase almost linearly from 0 to 37 vol% as the initial loading of the K-PG porogen was increased up to 40 wt%. The presence of the imprinted pores reduced the refractive index n and dielectric constant kvalues of the PMSSQ-BESSQB films almost linearly as the initial loading of the K-PG porogen was increased. These results lead to the conclusions that the sacrificial thermal decomposition of the K-PG porogen molecules successfully imprints nanopores into the PMSSQ-BESSQB dielectric films and that the population of the imprinted pores increases proportionally with increases in the initial loading of the porogen, up to concentrations of 40 wt%. The pore structures and properties of the nanoporous PMSSQ-BESSQB films imprinted by the K-PG porogen indicate that they are good candidates for use as interdielectric materials in the fabrication of advanced microelectronic devices.     

In-situ growth of mullite whiskers and their effect on the microstructure and properties of porous mullite ceramics with an open/closed pore structure

Porous mullite ceramics with an open/closed pore structure were prepared by protein foaming method combined with fly ash hollow spheres. Both the open porosity and total porosity of samples were enhanced by increasing the hollow sphere content. Mullite whiskers with a diameter of 0.2–4 μm were grown in-situ in the porous mullite ceramics with an AlF₃ catalyst, conforming to a vapor-solid growth mechanism. The pore structure of the porous mullite ceramics was significantly affected by the mullite whiskers which increased the open porosity and total porosity. Moreover, the median pore size was reduced from 65.05 μm to 36.92 μm after the introduction of mullite whiskers. The flexural strength and the thermal conductivity of the samples decreased with increasing total porosity. The porosity dependence of the thermal conductivity was well described by the universal model, providing a reference for the prediction of thermal conductivity of porous ceramics with open/closed pores.     

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.     

Role of Cenosphere Addition on Dielectric Properties of Sisal Fiber-Polypropylene Composites

This research investigates the influence of addition of porous additives on dielectric constant of polypropylene. Composite composed of PP matrix with sisal fiber having cylindrical pores and cenospheres having spherical pore, presents low dielectric constant. A new relation concerning porosity is proposed by modifying the usual mixing rule to predict the dielectric constant of PP composite. This research presents the dielectric properties of sisal fiber-reinforced PP composites with and with out cenospheres. Treated and untreated cenospheres with different concentration were loaded in chopped sisal fiber-reinforced polypropylene. The loading of the polypropylene with the sisal fiber, increases the dielectric constant ε′ and improves the ac conductivity σ_ac. The effect of temperature on the dielectric spectrum of polypropylene composites was investigated in the frequency range ranging from 1–10 kHz. Sisal fiber-reinforced polypropylene composites having 20% sisal fiber with and without cenospheres were developed and electrical properties such as dielectric constant (?′), dissipation factor (tanδ) and ac conductivity (σ_ac) of these composites were determined. Dielectric constant, tan δ, and a.c. conductivity increases with increase in temperature at different frequencies.     

Effect of Porosity in Catalyst Layers on Direct Methanol Fuel Cell Performances

Effects of porosity of catalyst layers (CLs) on direct methanol fuel cell (DMFC) performances are investigated using silicon dioxide (SiO₂) particles as a pore former. The pore size and volume of CLs are controlled by changing the size and content of SiO₂. As the size of pore formed by removal of SiO₂ increases, DMFC performances are enhanced. The augmentation in performances can be explained by facilitation of fuel transport to catalyst particles, increase of utilization efficiency of catalysts, diminishment in methanol crossover, reduction in activation loss and facilitation of water discharging out of CLs of cathode due to the controlled porosity in CLs. The enhanced fuel transport, accessibility of fuels to Pt catalyst surface, is proved by the active areas of Pt catalyst. In addition to the active area of Pt catalyst, porous CLs exhibit a decline in methanol crossover, leading to increase of open circuit voltage (OCV). The porous CLs also show improvements in activation loss due to high porosity, causing enhancement in DMFC performances. In aspect of pore volume contribution to cathode performance, the SiO₂ content is optimized. Based on the DMFC performances, it can be suggested that the optimum conditions of SiO₂ are 500 nm in size and 20 wt.% in content. The porosity effect on both electrodes appears as follows: the pores in cathode are more effective on DMFC performances (55.5%) than those of anodes (44.5%) based on the maximum power of DMFC, indicating that the pores in CLs facilitate removal of water from electrodes.     

Mechanical properties of porous ceramics in compression: On the transition between elastic,brittle, and cellular behavior

This paper deals with the uniaxial compression behavior of porous ceramics within a wide range of porosity, varying from 30 to 75 vol%. The load–displacement curves recorded on porous alumina samples showed a transition between a typical brittle behavior at porosity fractions below 60 vol% and a damageable, cellular-like behavior, at higher porosity fractions. This transition in fracture mode was confirmed by in situ compression tests in an X-ray tomograph. Based on a simple model taking into account the competition between the crack length initiating from spherical pores and the mean distance between pores, the porosity at which the transition took place was estimated. The influence of the pore size also depended on the volume fraction of pores: no size effect was noted at the lowest porosity whereas a statistical effect on the size of the solid walls was observed at higher porosity, with an increase in fracture strength with small pores.     

Highly porous barium strontium titanate (BST) ceramic foams with low dielectric constant from particle‐stabilized foams

A novel method for fabrication of highly porous barium strontium titanate (BST) ceramic foams based on particle‐stabilized foaming method was developed for the first time, in which propyl gallate (PG) was employed as BST particle modifier. The results showed that the stability of wet BST foams closely depends on the pH value and PG concentration, which could be explained by the adsorption behavior of PG on BST particle surface. BST ceramic foams with dense, uniform, and closed pore and defect‐free wall were obtained. The pore size and porosity can be well controlled by adjusting solid loading and sintering temperature. It was revealed that not only sintering temperature but also solid loading significantly influenced the growth of BST grain. The BST ceramic foams exhibited high porosity in the range of 81%‐95%, low dielectric constant in the range of 47‐150, and low dielectric loss below 0.0025. The BST ceramic foams with higher porosity presented a tendency of lower dielectric constant and the fitting results indicated that the natural logarithm of dielectric constant was linear correlated with porosity.     

Effects of nano-alumina content on the formation of interconnected pores in porous purging plug materials

The physical properties and microstructure of porous purging plug materials added with different nano-alumina contents and firing temperatures were investigated by means of X-ray diffraction, scanning electron microscopy, air permeability, pore size distribution, mean pore size, apparent porosity, bulk density, and cold crushing strength (CCS) tests. The results showed that the addition of nano-alumina had a great effect on the physical properties and microstructure of the porous purging plug materials. With increasing nano-alumina content in the composition, the main phase was α-Al₂O₃ in all compositions and the mean pore size, apparent porosity and air permeability all increased due to the increased number of pores and pore size of the specimens which facilitated the formation of interconnected pores. When the sintering temperature was changed from 1550 °C to 1650 °C, some of the smaller pores vanished due to solid phase sintering, which reduced the apparent porosity, and some open pores connected to form interconnected pores, which promoted increased air permeability. In addition, the strength and porosity were found to follow the relationship σ = σ₀ exp (-b P). When the apparent porosity increased, the CCS decreased, and vice versa.     

Factors controlling surface morphology of porous polystyrene membranes prepared by thermally induced phase separation

A special device for preparing porous polymer membranes through a thermally induced phase separation (TIPS) process was designed and machined; it included a solution container, a membrane‐forming platform, a coldplate, a temperature‐decreasing system and a temperature‐supervising system. Polystyrene was selected as the model polymer from which to prepare porous membranes using the device due to its better understood TIPS and good biocompatibility with cells. The major factors controlling surface morphology and cell size, ie volume fraction of polystyrene (ϕ₂), quench rate and solvent‐removing methods, were studied. Fixing the coldplate temperature, when ϕ₂ is as low as 0.045, provokes the formation of round pores on both the bottom and top surfaces of the membrane; when ϕ₂ = 0.16 no pores are formed on either surface; when ϕ₂ = 0.087 pores form on the top surface, but not on the bottom surface. When ϕ₂ = 0.087 the cell size is very small or no pores are formed on the bottom surface, whereas the top surface shows a regular decrease of the pore sizes and an increase of the pore number and pore area, along with a decrease of the coldplate temperature. The side near the coldplate is dense, and the dense layer aligns along the coldplate, while the side away from the coldplate is like a porous foam, the shape of which is isotropic and the surfaces are interconnected with each other three dimensionally. On the top surface of a membrane obtained by ethanol extraction, the cell size is enlarged and the cell number reduced, but the surface morphology and the whole area remained almost the same when compared to samples obtained by freeze drying in the same membrane‐forming conditions. The isotropic, uniformly distributed and round pores suggest that the mechanism of phase separation is a spinodal liquid–liquid decomposition under our research conditions. © 2000 Society of Chemical Industry     

Effects of Pore Morphology and Grain Size on the Dielectric Properties and Tetragonal–Cubic Phase Transition of High-Purity Barium Titanate

The effects of pore morphology and grain size on the dielectric behavior of high-purity stoichiometric BaTiO₃ have been intensively investigated. It was found that the dielectric constant was influenced not only by grain size but also by pore morphology. Dielectric constants below the Curie temperature could be evaluated by the Maxwell relationship for specimens with fractional density >90%ρ_t and be estimated by the modified Niesel's equation, but depolarization might be involved for specimens with fractional density <90%ρ_t. Dielectric Behavior above the Curie temperature followed the Curie–Weiss low. The Curie constants could be separated into two regions depending on the pore morphology, decreasing linearly with increasing porosity at different rates. The results suggest that the tetragonal–cubic phase transition temperature of specimens with fractional density <90%ρ_t is affected by depolarization due to the presence of continous channel pores. The dissipation factor was increased with increasing porosity due to the adsorption of water. In this study, a high-density (<99%ρ_t), uniform, and fine-grained (∼1.2 μm) microstructure of high-purity stoichimetric barium titanate has been produced by using wet processing ad pressureless sintering, in which a high dielectric constant (>6100 at 25°C and 1 kHz) and a low dissipation factor (<0.025) could be achieved.     

Polymer-derived porous ceramics from novel silicon-based preceramic/sucrose systems

Porous Si/C/O/(N) ceramic bodies were developed by the direct consolidation of novel liquid silicon-based preceramic polymer/porogen (methacryloxypropyl silsesquioxane/sucrose) systems, burnout, and N₂ pyrolysis (1300–1500 °C), and they were characterized via open porosity, volumetric shrinkage, and mass loss measurements. The evolution of phases as temperature increased was analyzed using XRD, TGA-mass spectrometry tests, and ²⁹Si NMR. The free carbon phase was characterized via Raman spectroscopy, and its content was determined using a carbon analyzer. Porous microstructures were analyzed by SEM/EDS and Hg-porosimetry, and by measuring the N₂ adsorption/desorption and specific surface area. The final ceramics exhibited a hierarchical porosity composed of large irregular pores that grew with temperature, together with a lower volume of meso- and micropores. β-SiC whiskers and faceted hexagonal crystals of α-Si₃N₄ were observed inside of cavities. The presence of meso- and micropores explained the high specific surface area achieved in the material pyrolyzed at 1500 °C.     

Preparation and characterization of 2‐hydroxyethyl methacrylate‐based porous copolymeric particles

2‐Hydroxyethyl methacrylate was copolymerized with three different comonomers, methyl methacrylate (MMA), styrene (St), and N‐vinyl‐2‐pyrrolidone (NVP), respectively, to prepare porous particles crosslinked using ethylene glycol dimethacrylate (EGDMA) in the presence of an organic solvent, 1‐octanol (porogen), by means of suspension copolymerization in an aqueous phase initiated by 2,2‐azobisisobutyronitrile. Nano‐pores were observed in the particles. The pore size and the swelling properties of these particles can be controlled by changing comonomers or adjusting the crosslinker or porogen concentration. A lower crosslinker or porogen concentration favors generating smaller pores, whereas a higher concentration of a hydrophilic comonomer, higher concentration of crosslinker, and higher porogen volume ratio promote the generation of larger pores. In addition, the effects of the porous characteristics on the swelling properties were explored. The swelling capacity of the porous particles is reduced with the increase in the crosslinker concentration; however, there is a critical porogen volume ratio, in which the maximal swelling capacity is reached. Higher porosity in the particles and higher amount of hydrophilic comonomer favor a higher swelling capacity of the particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007