Hierarchically porous alumina ceramic catalyst carrier prepared by powder bed fusion

Hierarchical porous ceramic catalyst carriers, which exhibit good catalytic performance, are widely used in the petrochemical industry. However, the fabrication of ceramic carriers with hierarchically porous structures is highly challenging for conventional preparation processes. Thus, a strategy for designing and manufacturing hierarchically porous alumina ceramic catalyst carriers using aluminium trihydrate as raw material and powder bed fusion (PBF) as the forming process is proposed herein. PBF process parameters were optimised to define the processing window for creating ceramics with complex structures. Controllable pore characteristics in nano- and microscales has been achieved by combining dehydroxylation, PBF, and post-sintering processes. The effects of raw material composition and process parameters on crush strength, porosity, and specific surface area were systematically investigated. The resulting porous ceramics exhibit a crush strength of 86.03 ± 18.10 N/cm, specific surface area of 1.958 ± 0.123 m²/g, and porosity of 64.85 ± 1.15% with a multipeak distribution at 95 ± 1.23 nm and 17.76 ± 0.14 μm. The possibility of complicated monolithic catalyst carrier structures with bionic leaf vein characters has been validated for potential industrial applications.     

Hierarchically porous ceria with tunable pore structure from particle-stabilized foams

We firstly fabricated CeO₂ ceramic foams with tunable structure by using particle-stabilized bubbles as template, and designed their interconnected porous structure and even hierarchically porous structure, which endows them the penetration ability for gases or liquids. Hollow spheres with single-layer shell were innovatively selected as the pore-former, which allows for the formation of open pores on the cell wall. Moreover, 3D printing CeO₂ particle-stabilized foams are realized with the aid of direct ink writing, which enables the production of CeO₂ ceramic foams with complex shape. Highly porous CeO₂ with relatively high compressive strength have been fabricated, the porosity of which varies from 81.0% to 92.0% while their excellent compressive strength ranges from 5.0 MPa to 20.0 MPa. Attributed to the hierarchical porous structure, uniform pore size distribution as well as densely assembled cell wall, 3D printing CeO₂ ceramic foams possess superior mechanical performance at high porosity level.     

Compound surfactant-based emulsion method for the preparation of high-porosity alumina microspheres

Porous alumina microspheres have attracted significant attention owing to their high mechanical strength and excellent chemical and thermal stability. The emulsion method is considered as a simple and controllable method for the preparation of inorganic microspheres. However, preparing alumina microspheres with the emulsion method is challenging because the emulsification of the precursor is inhibited by the rapid hydrolysis of aluminum alkoxide. Herein, we report a new emulsion method for the preparation of high-porosity alumina microspheres using a combination of ionic and non-ionic surfactants; in this method, the compound surfactants act as a template agent to guide aluminum alkoxide to form a lamellar structure through self-assembly. The decomposition of the templating agent and transformation of the alumina crystal at a high temperature result in structural collapse and formation of lamellar pores. Compound surfactants increased the spheroidization rate of the emulsion from 47% to 63% after hydrolysis, whereas the particle size was decreased by almost half. Additionally, the morphology and porosity of the alumina microspheres were changed. With increasing anionic surfactant content, the porosity increased initially and then decreased. The porosity of the alumina microspheres reached a maximum value of 76% at the 1:1 mass ratio of the non-ionic to anionic surfactants. Heat treatment was found to change the size of lamellar pores, with the pore diameter reaching maximum value at 1300 °C. The compound surfactants also increased the compressive stress and specific surface area of the porous alumina microspheres.     

Synthesis of hierarchical ZSM-5 microspheres with superior performance for catalytic methanol-to-olefin conversion

Methanol-to-olefin (MTO) conversion on zeolites has encountered severe coke deposition and rapid deactivation. Creating different levels of porosity is essential to mitigate such issues. Herein, we demonstrate a facile and green strategy to synthesize uniform and hierarchically macro/mesoporous ZSM-5 microspheres by combining spray-freeze drying and steaming-assisted crystallization (SAC). The structure, crystallinity, and porosity of the zeolite microspheres are controlled by adjusting the water/gel mass ratio and time in the SAC process. The structure evolution during the SAC process is revealed. In the catalytic MTO reaction, the representative hierarchically porous ZSM-5 catalyst exhibits superior catalytic performance. At a very high weight hourly space velocity of 18 h⁻¹, it shows a dramatically prolonged lifetime (47 h at >99% conversion) and much-improved selectivity to ethylene and propylene compared with the conventional microporous ZSM-5 and nano-sized ZSM-5. The enhanced performance is originated from the hierarchical structure and suitable acidity of the ZSM-5 microspheres.     

Porous mullite ceramics with enhanced compressive strength from fly ash-based ceramic microspheres: Facile synthesis,structure, and performance

Porous mullite ceramics are widely used in heat insulation owing to their high temperature and corrosion resistant properties. Reducing the thermal conductivity by increasing porosity, while ensuring a high compressive strength, is vital for the synthesis of high-strength and lightweight porous mullite ceramics. In this study, ceramic microspheres are initially prepared from pre-treated high-alumina fly ash by spray drying, and then used to successfully prepare porous mullite ceramics with enhanced compressive strength via a simple direct stacking and sintering approach. The influence of sintering temperature and time on the microstructure and properties of porous mullite ceramics was evaluated, and the corresponding formation mechanism was elucidated. Results show that the porous mullite ceramics, calcined at 1550 °C for 3 h, possess a porosity of 47%, compressive strength of 31.4 MPa, and thermal conductivity of 0.775 W/(m?K) (at 25 °C), similar to mullite ceramics prepared from pure raw materials. The uniform pore size distribution and sintered neck between the microspheres contribute to the high compressive strength of mullite ceramics, while maintaining high porosity.     

Preparation and performance of lightweight porous ceramics using metallurgical steel slag

In this paper, porous ceramics with high porosity and low bulk density were prepared by using steel slag and kaolin as main raw materials and polyurethane sponge as template. The effects of steel slag particle size, zirconia addition, the solid content of the slurry, and the addition of polycarboxylic acid water-reducing agent on the properties of ceramics were studied. In addition, by adding a surfactant (Sodium dodecyl sulfate) to form fine pores on the original framework of the three-dimensional network porous ceramic, the shortcomings of the single as well as the uncontrollable density and porosity of the porous ceramic, which are produced by the template method, are improved. When the grinding time of steel slag is 90 min, the content of zirconia is 3% wt, the solid content of ceramic slurry is 64% wt, and 0.6% wt polycarboxylic acid water-reducing agent and 0.4% of surfactant are added, the prepared porous ceramic skeleton is clear and good. The porous ceramic has a low bulk density (as low as 157.869 kg/m³), high porosity (about 94.05%) and high compressive strength (0.2 MPa). The crystalline phase of it is mainly composed of anorthite, gehlenite, forsterite and quartz. The addition of zirconia, water-reducing agent and surfactant only changes the macrostructure of porous ceramics, and does not change its crystal phase composition. The preparation of porous ceramics from steel slag not only solves the recycling problem of steel slag, but also provides a good substitute for main raw materials of porous ceramics.     

A simple route to prepare pomegranate‐like polystyrene‐based microspheres with high porosity

Pomegranate‐like polystyrene‐based microspheres with high porosity were successfully prepared via a simple route involving two steps. The first step was the preparation of polystyrene‐based microspheres with multi‐cores and a non‐porous shell via suspension polymerization of divinylbenzene and vinylbenzyl chloride. Nitrogen sorption failed to characterize the pore structure of the microspheres because of the non‐porous shell, but the results of Hg intrusion indicated that the pore volume of the microspheres was 0.36 cm³ g^?1. The second step was post crosslinking of the microspheres derived from the first step. Extensive porosity was generated in the shell and the pomegranate‐like structure of the microspheres remained almost unchanged. The results showed that the pore volumes of the final products derived from N₂ sorption and Hg intrusion were 0.54 cm³ g^?1 and 0.66 cm³ g^?1, respectively. Overall, this provides a simple and feasible route to biomimetic preparation of pomegranate‐like polystyrene‐based microspheres with high porosity. Copyright © 2011 Society of Chemical Industry     

Perfluoroalkyl-Functionalized Hyperbranched Polyglycerol as Pore Forming Agents and Supramolecular Hosts in Polymer Microspheres

Perfluoroalkyl-functionalized, hyperbranched polyglycerols that produce stable microbubbles are integrated into a microfluidic emulsion to create porous microspheres. In a previously-presented work a dendrimer with a perfluorinated shell was used. By replacing this dendrimer core with a hyperbranched core and evaluating different core sizes and degrees of fluorinated shell functionalization, we optimized the process to a more convenient synthesis and higher porosities. The new hyperbranched polyglycerol porogens produced more pores and can be used to prepare microspheres with porosity up to 12% (v/v). The presented preparation forms pores with a perfluoroalkyl-functionalized surface that enables the resulting microspheres to act as supramolecular host systems. The microspheres can incorporate gases into the pores and actives in the polymer matrix, while the perfluoroalkylated pore surface can be used to immobilize perfluoro-tagged molecules onto the pores by fluorous-fluorous interaction.     

Preparation and properties of porous ceramics from nickel slag by aerogel gelcasting

To further resource industrial solid waste, porous ceramics with high porosity were prepared by a gelcasting method using nickel slag and kaolin as raw materials and hydrophilic nontoxic SiO₂ aerogel as a gelling agent. The effects of nickel slag content, dispersant and solid content on the properties and microstructure of porous ceramics were investigated in detail in terms of density, compressive strength, porosity, phase composition and micromorphology. The results confirmed that a certain amount of nickel slag can effectively improve the porosity of porous ceramics, while the addition of dispersant can promote the flow of the slurry, enhanced the denseness of the raw billet and significantly improved the compressive strength. However, its excessive use had a negative effect on the ceramic density and porosity. At the same time, the solid content played a key role in the performance of porous ceramics prepared by gelcasting, and too much solid content was also not conducive to the generation of pores. When the nickel slag content was 55%, the amount of dispersant was 2%, and the solid content was 60 vol%, the porous ceramic had a better overall performance, the density of the porous ceramic was 510 kg/m³, the compressive strength was 1.3 MPa, and the porosity reached 80.1%. The major crystalline phases of porous ceramics prepared by nickel slag were cordierite and anorthite.     

复乳液滴模板法结合溶剂去除法制备P(MMA-MAA)超大孔聚合物微球

以聚(甲基丙烯酸甲酯-甲基丙烯酸)[P(MMA-MAA)]为主要微球材质,两亲性聚(乳酸-聚乙二醇)二嵌段共聚物(PELA)为辅助材质,通过复乳液滴模板法结合溶剂去除法,制备了微米尺度贯穿孔道结构的超大孔P(MMA- MAA)微球,考察了油相中材质浓度、内水相盐浓度、复乳演变时间等对微球形态及孔道结构的影响,分析了微球表面孔隙的演变机理. 在P(MMA-MAA)浓度100 g/L和PELA浓度30~40 g/L、外水相PVA浓度25 g/L、内水相NaCl浓度1~5 g/L、乳液熟化时间0~30 min的条件下,可制备出形态较好的超大孔微球,微球的表面孔径可达数微米,孔隙率最高可达95%. 超大孔微球形成后,对其骨架进行共价交联,可形成刚性微球骨架.     

Aerogel-like ceramic foams with super-high porosity and nanoscale cell wall from sol nanoparticles stabilized foams

Ultralight ceramic foam materials with high porosity play an important role in increasingly hi-tech areas due to the combinative merit of ceramic material and highly porous structure. So far, it remains challenging to fabricate alumina ceramic foams with extremely high porosity and high specific surface area that are comparable to aerogel materials by employing a low cost, eco-friendly and convenient approach. For the first time, we propose the preparation of aerogel-like ceramic foams with nanoscale cell wall and unprecedentedly high porosity using boehmite sol as both ceramic source and bubble interface stabilizer, based on sol nanoparticles stabilized foams using sodium lauryl sulfate (SDS) as modifier. The obtained ultra-stable sol foams allow for the achievement of bulk foams with ultrathin cell wall with thickness in the range of 30-90 nm, super-high porosity up to 99%, and large specific surface area of 280 m²/g, which is attributed to the well-organized assembly of nanoparticles at the liquid/air interfaces. This novel foam material demonstrates excellent adsorption ability for polar volatile organic gases (VOCs) due to its extremely high porosity and large specific surface area.     

Synthesis of monodisperse porous poly(divinylbenzene) microspheres by distillation-precipitation polymerization

Highly crosslinked monodisperse porous poly(divinylbenzene) (PDVB) microspheres were prepared by distillation-precipitation polymerization in acetonitrile containing up to 25 vol% of toluene as porogen with 2,2′-azobisisobutyronitrile (AIBN) as initiator in the absence of any stabilizer or surfactant. The porous polymer microspheres were formed through a precipitation manner during the distillation of the solvent from the reaction system. Monodisperse porous polymer particles with spherical shape and smooth surface were synthesized with diameters in the range of 1.86 and 3.06 μm, total porosity of up to 0.30 cm³/g and specific surface area as high as 762 m²/g. The growth procedure of porous PDVB microsphere was characterized by SEM technique for morphological observation and isotherm nitrogen adsorption for the determination of the special surface area and porosity. The resultant porous polymer microspheres had a novel structure with the gradual increasing of pore volume during distillation of the solvent out of the reaction system.     

5-FU-PLGA复乳微球的制备及体外释放

采用乳化溶剂挥发法制备W/O/W型5-FU-PLGA复乳微球,采用单因素设计考察了第一相体积比(内水相与油相)、第二相体积比(初乳与外水相)对复乳稳定性的影响,采用正交设计考察了搅拌温度、搅拌时间、辅料浓度和有机相中载体材料浓度对微球质量的影响,并对制备条件进行优化。最适宜制备条件为:第一相体积比为1:2,第二相体积比为1:1,搅拌温度为10 ℃、搅拌时间为6 h、辅料浓度为0.5%、有机相中载体材料浓度为15%。依据最适宜条件制备的微球圆整度良好、粒径范围窄,平均粒径5.20 μm,载药量为5.34%,包封率为77.22%。体外释放试验表明微球具有明显的缓释效果,释放行为符合Higuchi模型。     

Generation of meso- and microporous structures by pyrolysis of polysiloxane microspheres and by HF etching of SiOC microspheres

The porosity of polysiloxane microspheres obtained by emulsion processing of variably modified polyhydromethylsiloxane (PHMS) and subjected to pyrolysis in an Ar atmosphere at 450–650 °C was studied. Materials having micro- and mesopores with specific surface areas (SSAs) of up to 786 m²/g and pore volumes of up to 0.35 cm³/g were obtained. A high porosity was displayed by the microspheres heated at 600 °C that underwent deep depolymerization processes. Some polysiloxane microspheres were ceramized at temperatures of 1200–1500 °C and were subjected to etching by 35% aqueous HF. The microspheres heated to 1200–1400 °C were free of microcracks, whereas those ceramized at 1500 °C showed microcracks and macropores, although they preserved their spherical structure well. All of the microspheres ceramized at temperatures of 1200–1400 °C had low porosity. HF etching granted high micro- and mesoporosity to the materials ceramized at 1300–1500 °C. Microspheres heated at 1500 °C showed specific surface areas above 1000 m²/g after etching. These microspheres had low oxygen contents and were mostly composed of silicon carbide. Since they also showed macroporosity, HF etching of the polysiloxane microspheres ceramized at 1500 °C could be used to obtain hierarchically mesoporous-macroporous ceramic microspheres.     

Fibrous ceramic membrane constructed by mullite whiskers for the treatment of oil-in-water emulsions

Ceramic membranes with high porosity and excellent separation efficiency are necessary for the efficient treatment of large-scale wastewaters. However, the conventional ceramic membranes are usually prepared by particles-packing, which inhibits the advances of separation efficiency because of the low porosity and connectivity. Here, a fibrous ceramic membrane with mullite whiskers-interlocked structure was prepared by gas-solid reaction. The effects of aluminum fluoride (AlF₃) on the formation and growth of mullite whiskers, and then the permeability and selectivity of the ceramic membranes were investigated. With the increase of AlF₃ contents, the mullite phase evolved from needle-like, rod-like to flake-like structure, thus the catalyst accelerated the growth of mullite whiskers in the diameter direction. For the ceramic membrane sintered at 1400°C, the porosity increased from 58% to 76% while the average pore sizes increased from 0.65 to 3.93 μm because of the whisker-constructed structures. For the ceramic membrane sintered at 1450°C, the emulsion flux increased stably from 295 L/(m²·h) to 992 L/(m²·h) with the increase of trans-membrane pressure, and the oil rejection exceeded 98%. Thus, this study provides a feasible strategy for the preparation of ceramic membranes with high porosity and excellent separation performances.     

Molecularly imprinted polymer microspheres derived from pickering emulsions polymerization in determination of di(2‐ethylhexyl) phthalate in bottled water samples

The mono‐dispersed macroporous Molecularly Imprinted microspheres (MIPMs) selective for Diethylhexyl Phthalate (DEHP) were synthesized by Pickering emulsion polymerization. Silica nanoparticles were stabilizers in forming a stable oil‐in‐water emulsion, while the polymeric system was prepared by radical polymerization using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross‐linker. The results of scanning electron microscopy and nitrogen adsorption desorption measurement indicated that the obtained polymer microspheres had regularly porous structure and narrowly diameter distribution (100 nm), besides the specific surface area (S_BET) was 452 m² g^?1, pore volume was 9.685 cm³ g^?1, and pore diameter was 5.089 nm. The equilibrium adsorption capacity of MIPs was 1.75 mg g^?1 at 298 K. Good selectivity for DEHP in another two kinds of analogies (DBP and DAP) was demonstrated with high selectivity coefficients, respectively 17.753 and 19.450. In the end, DEHP‐MIP was used as packing of solid‐phase extraction to form an sensitive analytical method in extraction and enrichment DEHP in bottled water samples with the limits of detection of 1.7–2.5 μg L^?1.The recoveries at three spiking level (0.05, 0.1, and 1 mg L^?1) were varied between at 97.5 and 103.1% with RSD values below 3.5. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43484.     

Nano fibrillated cellulose-based foam by Pickering emulsion: Preparation,characterizations, and application as dye adsorbent

An ecofriendly and biodegradable porous structure was prepared from drying aqueous foams based on nano fibrillated cellulose (NFC), extracted from softwood pulp by subcritical water/CO₂ treatment (SC-NFC). The primary aim of this work was to use the modified SC-NFC as stabilizer for a water-based Pickering emulsion which upon drying, yielded porous cellulosic materials, a good dye adsorbent. In order to exploit the carboxymethylated SC-NFC (CMSC-NFC, with a degree of substitution of 0.35 and a charge density of 649 μeqv/g) as a stabilizer for water-based Pickering emulsion in subsequent step, an optimized quantity of octyl amine (30 mg/g of SC-NFC) was added to make them partially hydrophobic. A series of dry foam structures were prepared by varying the concentrations of treated CMSC-NFCs and 4 wt% was found to be the optimum concentration to yield foam with high porosity (99%) and low density (0.038 g/cc) along with high compression strength (0.24 MPa), superior to the conventionally extracted NFC. The foams were applied to capture as high as 98% of methylene blue dyes, making them a potential green candidate for treating industrial effluent. In addition, the dye adsorption kinetics and isotherms were found to be well suited with second order kinetics and Langmuir isotherm models.     

Alumina foam microspheres by emulsion drop-casting in aqueous ammonium chloride solution

A facile method for the preparation of alumina foam microspheres from hydrogenated vegetable oil-in-aqueous alumina slurry (HVO-in-AAS) emulsions is reported. The HVO-in-AAS emulsions drop-cast in cold aqueous NH₄Cl solution undergo fast gelation due to the freezing of HVO, physical cross-linking of carrageenan gelling agent and coagulation by NH₄Cl. Emulsions of HVO to AAS volume ratios of 1.5–2.5 prepared from 10 and 20?vol% AAS are used for drop-casting. Microspheres with sphericity close to 1 are obtained by drop-casting in 5?wt% aqueous NH₄Cl solution at ?3?°C. The well-defined interconnected cellular structure observed in the core of the sintered alumina foam microspheres is distorted towards the surface due to emulsion destabilization by the NH₄Cl. The porosity and cell size of the sintered alumina foam microspheres are independent of drop-casting bath conditions but depend on the emulsion composition. The microspheres have diameter, open pore volume and average cell sizes in the ranges of 2.38–2.49?mm, 1.22–2.42?cm³/g and 15.66–6.87?µm, respectively.     

Microfluidic fabrication of ZrO2 microspheres using improved external gelation aided by polyacrylamide networks

Microfluidic generation of emulsion microdroplets, combined with external gelation, is a promising method for the continuous production of high-quality ceramic microspheres. However, the external gelation mode is sensitive to the environmental concentration of sol-gel triggering agent, resulting in gel deformation due to uneven infiltration and reaction within the sol microdroplets. In this work, a polyacrylamide (PAM) gel network was used to prevent the microdroplets from undergoing apparent deformation throughout the gelation process, and dense ZrO₂ microspheres with high monodispersity and sphericity were fabricated successfully. Importantly, owing to the assistance of PAM network, the external gelation process becomes less sensitive and can be treated with a substantially higher triggering agent concentration, thus allowing a faster and more efficient sol-gel production of ZrO₂ ceramic microspheres.     

3D printing boehmite gel foams into lightweight porous ceramics with hierarchical pore structure

We herein report a novel hierarchically porous ceramic foams derived from boehmite gel foams, which possess both high porosity and superior strength. The gel foams show excellent printability due to its predominant stability, high yield stress and storage modulus, which endows such foam material ideal ink for 3D printing lightweight and complex-shape materials via direct ink writing approach. The 3D printed ceramic foams possess programmable architecture assembled by porous filaments, uniform macro-pores with tunable size in the range of 4∼70 μm, as well as nanoscale pores in cell wall, after sintering at relatively low temperature of 1200–1300 °C. In this way, ceramic foams with high strength were achieved, attributed to the tiny grains, large amount of grain boundaries, uniform pores and hierarchical pore structure. Notably, the foams sintered below 1200 °C have significant advantage on specific surface area, which could reach up to 300-400 m²/g.