The effect of washing process on the cracking of ZrO2 microspheres by internal gelation

ZrO₂ microspheres are widely used as a simulant of UO₂ in the development of nuclear fuel. However, the cracking of ZrO₂ microspheres prepared by internal gelation is still a challenge during drying and sintering processes. To address this issue, we designed and optimized the washing process for obtaining crack-free ZrO₂ microspheres. Through thermogravimetric, infrared, Raman, BET, and SEM analysis, it is shown that the cracking of the microspheres is mainly related to the pores in microspheres. The washing solvent with low surface tension is used to reduce the effect of capillary force on pore shrinkage. Therefore, the optimal washing process was designed as trichloroethylene (TCE)—0.5 M NH₃.H₂O—Propylene glycol methyl ether (PM) and gel microspheres with a high specific surface area of 315.3 m²/g and pore volume of 0.4125 cm³/g were obtained. The characterizations also further showed that when the microspheres were dried and sintered, the water vapor and the decomposition gas of organic matter were completely released from the pores in the microspheres. Our new washing process could be directly extended for preparing crack-free ceramic microspheres by internal gelation.     

Preparation of UC ceramic nuclear fuel microspheres by combination of an improved microwave-assisted rapid internal gelation with carbothermic reduction process

Uranium carbide (UC) ceramic microspheres filled into a cladding are a potential nuclear fuel format for nuclear reactors. Uniform sized ceramic UC microspheres with a diameter of 675?±?10?µm were successfully prepared by an improved microwave-assisted rapid internal gelation process combined with carbothermic reduction. First of all, the nanoparticle carbon was dispersed into the HMUR stock solution, and the C-UO₃·2H₂O gelled microspheres were prepared using an improved microwave-assisted internal gelation process without cooling the initial stock solutions. Next, the gelled microspheres were subjected to a carbothermic reduction process to obtain ceramic UC microspheres. TG and XRD investigations indicated that the C-UO₃·2H₂O microspheres were firstly reduced into UO₂ at a temperature of 700?°C, and were further converted into UC at 1500?°C in argon atmosphere. Crack-free ceramic UC microspheres with a smooth and metallic shiny surface were obtained at a sintering temperature of 1500?°C for 5?h with an initial C/U molar ratio of 3.5.     

Preparation of CeO2 microspheres by internal gelation process with copolymerization using acrylic acid

Cerium dioxide microspheres were successfully prepared by internal gelation process with copolymerization using acrylic acid. The effects of acrylic acid (AA)/hexamethylenetetramine (HMTA) molar ratio and concentration of solution containing urea and HMTA on the stability of precursor solution and on the prepared microspheres were investigated. The results indicated that acrylic acid could modify the urea resin and slow down the decomposition of urea resin. The stability of precursor solutions was improved with the increase of AA/HMTA molar ratio, but the surfaces of gelled microspheres became rough and cracked when the ratio was greater than 1. The solution containing urea and HMTA had a significant effect on the stability of precursor solution and on the surface morphology, specific surface area, pore volume and average pore diameter of the microspheres. The porous CeO₂ microspheres were obtained by heat treatment at 600?°C for 2?h.     

Fluidized state gelation of ceramic microspheres: Feasibility study of a continuous process and analysis of the chemical dehydration phenomena

A continuous gelation process for producing aluminum and zirconium hydroxide microparticles was conceived and tested in a lab‐scale apparatus. Fluidized state was devised as an appropriate hydrodynamic configuration to maintain the reacting sol microdrops suspended: stable non‐coalescing spherical gel particles in a size range quite below 100 μm were produced via gelation. The microspheres produced by a subsequent calcination step showed a diameter ranging between 2 μm and 20 μm. This powder, without further size classification, was an optimal product to manufacture test specimens by sintering. Measurements on the mechanical properties, such as toughness, flexural strength and hardness, classified the test bars as a very promising ceramic material. In order to enlighten the chemical drying phenomenon and devise the main governing mechanisms acting in the gelation reaction, an extremely simplified experimental system was set. A single drop of sol was deposited into a given amount of the dehydrating liquid medium and observed by an optical microscope; image analysis permitted us to identify the gel formation, the size reduction kinetics, as well as secondary phenomena.     

Preparation of monodisperse YSZ ceramic microspheres by high-throughput and instant-mixing droplet microfluidic system

The internal gelation process without cooling at room temperature is a significant challenge for the preparation of yttria-stabilized zirconia (YSZ) ceramic microspheres. In this work, a high-throughput and instant-mixing droplet microfluidic system that can prepare monodisperse YSZ ceramic microspheres was constructed. It mixed two stable solutions at room temperature in an active micromixer at a flow rate of mL/min, and then the mixed unstable precursor solution was quickly dispersed into sol droplets through a coaxial microfluidic device, and the droplets solidified into gel microspheres. The washed and dried gel microspheres could be sintered to obtain ceramic microspheres. Compared with no-micromixing and T-junction micromixers, the system had the best mixing performance and Y and Zr elements in the prepared ceramic microspheres were evenly distributed. Therefore, the system overcame the problem of precursor solution solidification and clogging of the device, and provided a new approach for the internal gelation process without cooling at room temperature.     

Ultrahigh-strength alumina ceramic foams via gelation of foamed boehmite sol

Ceramic foams with significant porosity and robust mechanical properties have received extensive attentions. However, it is still difficult to achieve excellent compressive strength at high porosity levels. In this work, a gelation of foamed boehmite sol method is proposed to settle this issue. The technological parameters during preparation process are systematically investigated. As-prepared alumina ceramic foams possess unprecedentedly high compressive strength of 34.1-89.1 MPa at high porosity levels of 66.0%-87.2%, which is attributed to the present of hierarchical pore structure, small grain size and pore size. This work demonstrates a facile and novel method for the fabrication of high-performance alumina ceramic foams toward practical applications.     

双乳化-凝胶法制备单分散海藻酸钙微球及其载BSA研究

采用双乳化-凝胶法制备了单分散的海藻酸钙凝胶微球,并通过正交试验系统考察了海藻酸钠浓度、氯化钙浓度、表面活性剂浓度、搅拌速度和油水比对海藻酸钙凝胶微球粒径及形貌的影响。在优化的条件下,制备出了平均粒径为4μm、单分散和球形度好的海藻酸钙凝胶微球。包埋模型药物牛血清白蛋白(BSA)的过程中,以去离子水作为洗涤液洗涤海藻酸钙微球时,BSA的包封率仅为13%左右;当水洗液的pH值为3.2时,BSA的包封率提高到66%左右,载药率可达16%,这是海藻酸钙pH值响应溶胀和BSA与海藻酸盐之间静电作用的结果。微球中BSA的体外释放曲线表明,该系统具有在模拟胃液中释药速率慢、释药量低、模拟肠液中释药迅速的特性。因此,双乳化-凝胶法制备海藻酸钙微球有望成为制备蛋白类药物控释制剂的一种新方法,以达到靶向快速给药的目的。     

Rapid preparation of hierarchically porous ceramic microspheres based on UV-curing-assisted molding

Ceramic microspheres have attracted significant attention, while the preparation of hierarchically porous ceramic microspheres with high porosity, good sphericity, and controllable size or shape in a short time remains a challenge. Herein, we developed a highly adaptable methodology for the preparation hierarchically porous ceramic microspheres with high porosity and favorable shape in a short time. The UV-curing assisted molding method combined with the Pickering emulsion method was utilized to prepare hierarchically porous ceramic microspheres. Under the irradiation of a UV-curing lamp (395 nm, 50 W), the Pickering emulsion can be cured within as short as 10 s. The microstructures of the three microspheres with different shapes were characterized by scanning electron microscopes (SEM). The as-prepared microspheres had a high sphericity, the interconnectivity of pores was as high as 54 %, and its porosity was as high as 73.4 % ± 3.0 %, while the density was quite low at ∼ 1.02 g/cm³.     

Microfluidic fabrication of ceramic microspheres with controlled morphologies

In this study, the diffusion‐induced external gelation is combined with a microfluidic technique to prepare monodisperse ZrO₂ ceramic microspheres. The gelation of sol droplets is traced by fluorescence visualization of the local pH, and it illustrates the effect of the external concentration of triggering agent (tetramethylethylenediamine, TMEDA) on the formation of the gel network, which results in 3 kinds of deformation of the gel particles. The deformation mechanism mainly lies in the imbalanced Laplace pressure exerted on the gel network during the competition between the gelation and the drying processes. By regulating the concentration of TMEDA, the monodisperse ZrO₂ ceramic microspheres with high sphericity can be readily fabricated.     

石蜡聚苯乙烯微球的制备Ⅲ.壁膜的选择及包覆研究

通过悬浮聚合技术合成了以聚苯乙烯为壁材、以石蜡为芯材的储能微球,研究了壁膜的选择及包覆程度。结果表明:聚苯乙烯很适合作为石蜡储能微球的壁膜,合成的石蜡聚苯乙烯微球包覆完整。     

Preparation of micron-scale monodisperse oil-in-water microspheres by microchannel emulsification

Micron-scale monodisperse oil-in-water (O/W) micropheres (MS) were prepared using a novel microchannel (MC) emulsification technique. The characteristics of the MS preparation and the O/W-MS prepared were studied. Soybean oil and medium-chain triacyglycerol (MCT) were used as the disprrsed phase, and physiological saline was used as the continuous phase. Silicon MC with 1 to 3μm-equivalent channel diameters were employed. A novel MC module was devised to easily recover the O/W-MS prepared. The effects of the channel shape on the behavior of MS formation, on the MS size, and on the distribution were investigated. An MC with a terrace at the MC outlet stably yielded micron-scale monodisperse O/W-MS; the MS had diameters of about 5 μm, and their coefficients of variation were below 9%. Monodisperse food-grade O/W-MS with diameters of about 4 μm could be obtained by using polyglycerol fatty acid ester as the surfactant. The size and size distribution of the recovered O/W-MS remained almost constant over 60 d, demonstrating their long-term stability.     

石蜡聚苯乙烯微球的制备Ⅱ.分散剂及复合介质的影响

通过悬浮聚合法合成了石蜡聚苯乙烯微球,研究了合成过程中复合介质的配比和用量以及分散剂种类和用量对微球粒径及其分布的影响。结果表明:采用聚乙烯醇作分散剂,更有利于合成小粒径高产率的石蜡聚苯乙烯微球,悬浮聚合体系中水-乙醇复合介质的最佳体积配比和用量分别为1:2.5和150mL。     

Monodisperse microspheres of copolymers of glycidyl methacrylate and its derivatives as materials for biomedical application

Monodisperse microspheres of copolymers of glycidyl methacrylate were prepared by dispersion polymerization in organic media. The microsphere diameter could be adjusted in the range from 0$md$5 μm to 5μm by changing the monomer concentration, the type of dispersion medium and the content of the comonomers. Terpolymers of glycidyl methacrylate, 2-hydroxyethyl methacrylate and tri(ethylene glycol) dimethacrylate were analysed by thermal decomposition gas chromatography and the compositions of the polymers agreed well with those of the monomer mixtures. The epoxide of the polymer microspheres was hydrolysed to α,β-diol with dilute sulphuric acid without side reactions except the slight formation of sulphate. It was confirmed by the ¹³CFT-NMR spectrum that the main structure of the hydrolysate was that of poly(glyceryl methacrylate). In the reaction of the epoxide with ammonia, the predominant production of tertiary amine was presumed by the relationship between the conversion of the epoxide and the nitrogen content of the reaction product. The amination of the epoxide with secondary amines resulted in the quantitative formation of the corresponding tertiary amines.     

一次盐水陶瓷膜装置的运行与改进

介绍了一次盐水陶瓷膜工艺的技术特点,总结了生产操作中的注意事项,分析了运行中发现的问题,并提出了改进措施。     

Fabrication of CeO2 microspheres by internal gelation process using flow-focusing droplet generator

Sphere-pac fuel is an alternative nuclear fuel technology in which microspheres of two or more sizes are utilized to fill the cladding tube in place of the more conventional single-size fuel pellets. This provides leeway for adjusting the fuel pellet packing density and resulting cladding tube porosity. The current investigation makes use of a flow-focusing droplet generator made from stainless steel (S.S.) 316 L, with a channel internal diameter (I.D.) of 0.5, 0.8, 1, and 3 mm. These microspheres were supposed to be of actinide oxide but here, cerium has been chosen as a surrogate of plutonium. Detailed information about the flow-focusing droplet generator, internal gelation process, and sphere-pac fuel has been provided. The size and size distribution of ceria microspheres were investigated by varying the flow rates of the continuous and dispersed phase. The characterization of ceria microspheres has been conducted using techniques such as scanning electron microscope (SEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and Brunauer–Emmett–Teller (BET) analyses. The size of prepared monodisperse microspheres was controlled precisely (within ±2%) in the range of 498–2888 μm using four S.S. 316 L flow-focusing droplet generators with channel I.D. 0.5, 0.8, 1, and 3 mm, respectively, and the coefficient of variation of the size distribution was found to be less than 2%.     

碱溶胀法制备核壳中空微球研究进展

综述了碱溶胀法合成核壳中空微球的国内外研究进展,重点介绍了核壳中空结构的合成以及各种因素如聚合物组成,碱处理条件、乳化剂用量、单体瞬时转化率以及玻璃化温度对微球形态的影响。     

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.     

Pore structure improvement in cermet for anode-supported protonic ceramic fuel cells

The porous cermet of Yb-doped BaZrO₃ and nickel (BZYb–Ni) for anode-supported protonic ceramic fuel cells (PCFCs) was fabricated by compression molding following the liquid condensation process (LCP). The gas permeability of BZYb–Ni produced by LCP (BZYb–Ni_LCP) was greater than that of BZYb–Ni produced by a conventional drying method (BZYb–Ni_CDM) although their porosities were similar. The greater permeability of BZYb–Ni_LCP than that of BZYb–Ni_CDM is consistent with more efficient structures for gas flow; a smaller specific surface area, and a larger critical diameter for pores in BZYb–Ni_LCP than those for pores in BZYb–Ni_CDM.     

铝溶胶的制备条件对其凝胶成球性能的影响

以硝酸和拟薄水铝石为原料制备了铝溶胶,考察了x(H+/Al摩尔比)和φ(六亚甲基四胺溶液与硝酸溶液的体积比)值对铝溶胶在油中凝胶成球性能的影响。使用氧化铝颗粒的Zingg指数对铝溶胶制备条件进行了评价。结果表明:铝溶胶和半透明铝溶胶的制备条件是x分别大于0.05和0.07;增大x和φ值均利于铝溶胶的凝胶化,但过大的x和φ值不利于溶胶收缩成球;Zingg曲线在1附近的平稳区间对应的x和φ值是合适的铝溶胶制备条件。     

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.