双重Pickering乳液法制备聚丙烯酰胺多孔微球及应用

采用亲水性气相二氧化硅N20和疏水性气相二氧化硅H30复配表面活性剂制备O/W/O型双重乳液,以此为模板,聚合中间相,挥发内相制备聚丙烯酰胺(PAM)多孔微球,并用于染料分子亚甲基蓝的吸附。结果表明：乳液显微镜照片显示水油比对双重乳液的形成有很大的影响,当水油比(O₁/W)/O₂为(1/2)/2时,可得到稳定的双重乳液;扫描电镜(SEM)照片显示PAM多孔微球基本呈球形,但粒径不均匀,球体表面粗糙,内部为空心结构;激光粒度仪(DLS)结果表明PAM微球平均粒径为356nm,多分散系数(PDI)为0.718,比表面积为230m²/g,粒径分布宽;在吸附温度35℃、吸附时间5min时对亚甲基蓝的吸附率为98.89%,最大吸附率超过99%,在吸附速率和吸附率上均优于传统PAM吸附剂,本研究为染料废水的处理提供了新方法。     

SiO_2和LiBr固体无机盐致孔剂制备多孔聚酰亚胺微球

在非水乳液体系中,以两步法为基础,采用固体无机盐(Si O2、Li Br)为致孔剂,经与聚合物PI结合、占位、脱除等步骤后成功制得多孔PI微球。通过红外光谱(FT-IR)、扫描电子显微镜(SEM)等手段来表征产物的化学结构和微观形貌。对于PI微球的球形和孔结构,从致孔剂的种类、加入时间和加入方式等方面进行了探讨。研究表明,2种无机盐对PAA亚胺化程度几乎没有影响,以溶液形式在聚合后加入反应体系,制得球形形貌最佳。与Li Br相比,Si O2致孔效果更好。     

3D gel-printing of hierarchically porous BCP scaffolds for bone tissue engineering

In this study, a conventional technique of porous preparation was used to improve the constructive capability of direct ink writing on microstructures, and the hierarchically porous scaffolds were successfully prepared by 3D gel printing (3DGP). Micron-sized hydroxyapatite (HA) was coated with tricalcium phosphate (TCP) nanopowders synthesized by chemical co-precipitation to form biphasic calcium phosphate (BCP). The random structure of concave micropores was achieved by filling the BCP slurry with PMMA microspheres while successfully controlling the internal porosity of printed filaments. The results showed that the three-stage porous structure was successfully constructed, i.e., macroscopic pores of 1.50–2.00 mm, spherical micropores of 100–200 µm, and inter-powder interstices of 1.00–10.00 µm. Nano-TCP coated micron-HA powders improved the sintering activity of BCP particles. The compressive strength and porosity of the scaffolds sintered at 1400 °C were 2.78 MPa and 84.98%. The hierarchically porous BCP scaffolds had bright applications in bone tissue engineering.     

泡沫相相分离制备多孔聚合物微球连续化工艺

采用在泡沫相进行溶剂挥发的方法，连续、高效制备聚甲基丙烯酸甲酯-丙烯酸丁酯[P(MMA-BA)]共聚物多孔微球。采用自制的连续化反应装置，在一定搅拌速率和反应温度下，向反应器连续加料，在出口处连续收集溢出的泡沫并进行消泡、分散，再经洗涤、过滤、干燥得到多孔聚合物微球。重点研究了油相进料速率、反应温度、搅拌速率、聚乙烯醇用量(PVA浓度)对平均泡沫溢出速率、微球收率、微球粒径以及多孔形态的影响规律。结果表明：在反应温度为45℃，搅拌速率为500 r/min，油相溶液进料速率为30 g/min，PVA浓度为1.0%(质量)，油相溶液中P(MMA-BA)∶二氯甲烷(DCM)∶正庚烷(HT)=10∶53∶6(质量比)的工艺条件下，聚合物微球的收率高达92%，平均粒径为130 μm，P(MMA-BA)微球球形饱满，呈多孔结构。     

肺部给药用高分子多孔微球的制备及改性研究进展

肺部给药作为一种非入侵式的给药方式,在蛋白质、多肽类药物的给药研究中具有很大的发展潜力。高分子多孔微球是最适合肺部给药的药物载体之一,本文首先阐述了高分子多孔微球的几种传统制备方法,分析了这些制备方法在不同的条件下存在的优点及缺点。随后本文针对传统的高分子多孔微球制备条件难以单独控制,药物不能有效包封等问题,对近年来研究者们为了提高多孔微球的性能对其进行的物理化学改性进行了综述并提出了观点。最后对肺部给药用高分子多孔微球不同的制备方法的相互结合以及在生物医学领域的应用价值进行了展望。     

Effect of pH and zeta potential of Pickering stabilizing magnetite nanoparticles on the features of magnetized polystyrene microspheres

Styrene as a monomer was emulsified in water using several magnetite nanoparticles concentration and pH values. Emulsified styrene drops were used as templates for polymerization, in presence of water soluble free radical initiator, and formation of composite particles. Styrene template drops stabilization was verified by light as well as scanning electron microscopy imaging, which ensured the participation of the particles in building up a mechanical barrier to stop oil drops coalescence. Furthermore, the produced polystyrene composites were strongly attracted to an external magnet. The difference in particles size as a function of pH was elucidated using zeta potential measurements, which indicated dominance of pH on the hydrophilicity of the particles and consequently the extent of emulsification, which in turn affected the size of the obtained microspheres. Under some circumstances, capsules were formed instead of particles. Thereby, it can be concluded that the magnetic microspheres are optimally formed at pH 2.3 independently of the magnetite content used.     

多孔陶瓷材料的制备研究进展

介绍了多孔陶瓷材料的分类、性能和应用,综述了多孔陶瓷的制备方法,并分析了不同制备方法的特点。     

Sugarcane bagasse as the scaffold for mass production of hierarchically porous carbon monoliths by surface self-assembly

The hierarchically porous carbon materials (HPCMs) with micro- and meso-porosity were prepared by surface coating and solvent evaporation-induced self assembly (EISA) using sugarcane bagasse as the scaffold. The triblock copolymer F127 and phenol-formaldehyde resin were used as mesostructural directing agent and carbon precursor, respectively. The microstructures in terms of morphology, pore texture, degree of graphitization, and thermal stability were characterized by scanning and transmission electron microscopy, nitrogen adsorption analysis, X-ray powder diffraction, and thermogravimetric analysis, respectively. The bulk morphology of HPCMs with hierarchically porous architecture can be retained after calcination at 1000 °C. Small and wide angel XRD patterns show 2-D hexagonal mesostructures and enhanced degree of graphitization. The specific surface areas of monolithic carbon materials are in the range 487-544 m² g⁻¹ with the micropore percentages of 66-67%. The thermal stability of HPCMs is enhanced by the strong interaction of hydroxyl groups of sugarcane bagasse with phenol-formaldehyde resins, and subsequently retains the highly ordered structures with pore size distributions centered at 0.5 and 3.2 nm. In addition, the bagasse-based HPCMs show good electrochemical property and the specific capacitances are in the range 190-234 F g⁻¹ at the scan rate of 5-50 mV s⁻¹. Results clearly show that the use of surface coating and EISA with sugarcane bagasse as the scaffold is an easy, effective and mass productive strategy for fabrication of HPCMs.     

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.     

Facile fabrication of nanocomposite microspheres with polymer cores and magnetic shells by Pickering suspension polymerization

Pickering suspension polymerization was used to prepare magnetic polymer microspheres that have polymer cores enveloped by shells of magnetic nanoparticles. Styrene was emulsified in an aqueous dispersion of Fe₃O₄ nanoparticles using a high shear. The resultant Pickering oil-in-water (o/w) emulsion stabilized solely by magnetic nanoparticles was easily polymerized at 70 °C without stirring. Fe₃O₄ nanoparticles act as effective stabilizers during polymerization and as building blocks for creating the organic–inorganic hybrid nanocomposite after polymerization. The fabricated magnetic nanocomposites were characterized by FTIR, XRD, TGA, DSC, GPC, XPS and SEM. The structures of the polymer core and the nanoparticle shell were analyzed. We investigated the effects on the products of the weight of Fe₃O₄ nanoparticles used to stabilize the original Pickering emulsions. Pickering suspension polymerization provides a new route for the synthesis of a variety of hybrid nanocomposite microspheres with supracolloidal structures.     

Fabrication of highly porous mullite microspheres via oil-drop molding accompanied by freeze casting

Porous mullite microspheres with a highly open porosity and average diameter of more than 800 µm were fabricated via an oil-drop molding method accompanied by a freeze casting process. After sintering, a highly porous structure was formed due to interlocking whisker-shaped mullite grains and formation of interconnected skeletons during the freeze-casting process. Additionally, it was found that a high porosity and large pore size in the microspheres green bodies are favorable for the synthesis of mullite whiskers with high aspect ratio.     

Waste recycling of coal fly ash: A novel approach to prepare hierarchically porous coal fly ash/Al2O3 ceramic composite with high porosity and high strength templated by emulsion-assisted self-assembly

The coal fly ash (CFA) produced from coal-fired power generation is classified as a common solid waste; thus, improving the recovery and utilization rate of CFA is highly desirable. In this study, a novel strategy using CFA and Al₂O₃ as raw materials, to prepare hierarchically porous ceramic composites that serve as potential candidates for future building materials is developed. In this process, the well-developed self-assembly method in which an anionic modifier is used to prepare hydrophobic powders that form an attractive oil/water network via electrostatic interactions, thereby yielding honeycomb-like structures. In order to explore the mechanism of preparation, five samples with different mixture ratios of alumina and CFA were prepared according to 1: 0, 2: 1, 1: 1, 1: 2, and 0: 1 (Alumina: CFA). Compared with the sample prepared with pure CFA, the as-prepared CFA/Al₂O₃ composite exhibited both superior porosity and high mechanical property. When the porosity is as high as 73 ± 0.17%, the compressive strength is as high as 80.9 ± 3.4mpa (alumina: CFA = 1:1). As the porosity decreases to 49.3 ± 0.7%, the compressive strength reaches 159.33 ± 36.89mpa (alumina: CFA = 1:2). Moreover, this work obtains the highest compressive strength-porosity related B-value in comparison to previously reported CFA-based composites and provides a new insight into the effective recycling of CFA and offers a novel approach to prepare CFA/Al₂O₃ composite with excellent overall mechanical properties.     

泡沫分离法制备聚苯乙烯多孔微球

以一种新型、简单、高效的溶剂挥发法制备不同孔形态和粒径分布的聚苯乙烯微球。该方法利用机械搅拌和升温过程中溶剂挥发产生的泡沫,将油相液滴夹带进入泡沫相,使溶剂在气相中迅速挥发,诱导聚合物与非良溶剂发生相分离成孔。结果表明：随着聚合物与致孔剂用量比减小,微球结构形态由多孔演变到中空结构;聚乙烯醇（PVA）质量分数由1%增大至3%时,微球的平均粒径由52μm±23μm减小至23μm±20μm及转速由300r/min增大至700r/min时,微球粒径由107μm±40μm减小到45μm±20μm,但由于产生的泡沫量和泡沫形态不同影响了溶剂的挥发过程,故得到微球的多孔形态不同,增大PVA浓度得到的微球表面孔数目较少、孔径较大,而增大转速得到的微球孔数目较多。此外,该方法在油水相比≥1时,在泡沫中也能得到稳定规则的多孔微球,而传统的在水相中引发相分离的方法因水相无法完全分散油相,故无法成球。     

Synthesis of silver/polymer colloidal composites from surface-functional porous polymer microspheres

This study presents a different colloidal silver (Ag)/polymer system where Ag nanoparticles are deposited uniformly onto surface-functional porous poly(ethylene glycol dimethacrylate-co-acrylonitrile) (poly(EGDMA-co-AN)) microspheres. The formation and morphology of the composite microspheres were characterized from electron microscopy and X-ray diffraction analyses. The significance of the present report is that owing to the high affinity between Ag and nitrile group (CN) on the large surface of the microspheres, the Ag nanoparticles having a face-centered cubic phase were incorporated evenly into the deep pores of the microspheres with fine size and size distribution. In the preservation test, the Ag/poly(EGDMA-co-AN) composite microspheres obtained showed an excellent anti-bacterial performance, elucidating a high applicability for a new preservative.     

二元溶剂体系对泡沫传输制备聚苯乙烯微球的影响

采用二氯甲烷（DCM）和丙酮（AC）组成二元溶剂体系,考察了二元溶剂体系对制备聚苯乙烯（PS）微球时泡沫的传输和微球性能的影响,并探讨了对应的作用机理。实验结果表明,随着AC质量分数的增加,体系的出泡温度升高,PS微球的平均粒径下降且粒径分布逐渐变窄,微球的结构由多孔逐渐演变为中空。这主要是由于AC对水具有一定的亲和性,会往连续相迁移,改变连续相的表面张力,并在油水界面形成一个AC/DCM的混合液膜层,该液膜层改变了溶剂挥发的过程,最终实现对微球粒径和结构的调控。     

堇青石多孔陶瓷制备及其性能优化研究进展

堇青石多孔陶瓷因具有高的孔隙率,优异的力学强度和良好的抗热震性能而被用作汽车尾气催化剂的载体材料.为此,综述了堇青石多孔陶瓷的制备方法和掺杂元素与其性能(孔结构、抗热震性和力学强度等)的相关性,同时指出了堇青石多孔陶瓷在制备过程中存在的问题,并展望了作为汽车尾气催化剂载体的堇青石多孔陶瓷未来的发展方向.     

无皂乳液聚合法合成单分散性阴离子聚苯乙烯微球

采用无皂乳液聚合法制备了粒径大小可控且均一的聚苯乙烯微球,研究了反应过程中SDS加入量、反应温度、引发剂加入量及反应介质对聚苯乙烯微球粒径大小及分布的影响。利用傅立叶变换红外光谱仪对微球结构进行了表征。     

微流体技术制备粒径可控且均一的SDB-TPGDA多孔微球

设计构建了可拆装的毛细管基微流体控制系统用于制备具有高度单分散性(CV值为3.78%)的苯乙烯(St)/二乙烯基苯(DVB)/三缩丙二醇双丙烯酸酯(TPGDA)多孔共聚物微球。所制备的单分散性多孔微球在直径250~1 550μm内通过调控分散相与连续相流量比及连续相黏度实现粒径精准可控。采用光引发聚合实现具有优良球形度微球(Max.D./Min.D.小于1.05)的快速在线制备,光引发聚合速率随着TPGDA在混合单体中质量的增加而增加。该研究提供了一种有效制备单分散性大粒径聚苯乙烯类多孔微球方法。     

Preparation of uniform magnetic recoverable catalyst microspheres with hierarchically mesoporous structure by using porous polymer microsphere template

Merging nanoparticles with different functions into a single microsphere can exhibit profound impact on various applications. However, retaining the unique properties of each component after integration has proven to be a significant challenge. Our previous research demonstrated a facile method to incorporate magnetic nanoparticles into porous silica microspheres. Here, we report the fabrication of porous silica microspheres embedded with magnetic and gold nanoparticles as magnetic recoverable catalysts. The as-prepared multifunctional composite microspheres exhibit excellent magnetic and catalytic properties and a well-defined structure such as uniform size, high surface area, and large pore volume. As a result, the very little composite microspheres show high performance in catalytic reduction of 4-nitrophenol, special convenient magnetic separability, long life, and good reusability. The unique nanostructure makes the microspheres a novel stable and highly efficient catalyst system for various catalytic industry processes.     

An improvement of microfluidic-assisted internal gelation in the preparation of millimeter-sized ceramic microspheres

The microspheres prepared by the microfluidic-assisted internal gelation process are still challenging to reach the millimeter size due to the large gravity. The gravity would affect the sphericity and size uniformity of microspheres. The improved microfluidic-assisted internal gelation process is designed and optimized to produce large-sized monodisperse ceramic microspheres with good sphericity. The movement mechanism of millimeter-sized sol droplets and gel microspheres in the microchannel is summarized and the state of the dispersed phase entering the measuring cylinder is controlled. The friction between the gel microspheres and the tubing wall is reduced as much as possible, and ZrO₂ ceramic microspheres of 500 ± 5 μm with good sphericity are prepared with the broth at room temperature. The mechanism of sol droplets entering the oil surface is explored to demonstrate the superiority of the improved microfluidic-assisted internal gelation process. The improved microfluidic-assisted internal gelation process could be directly extended to preparing other millimeter-sized monodisperse ceramic microspheres.