自组装制备PEG接枝聚苯乙烯微球的粒径控制

用苯乙烯封端的聚乙二醇(St—PEG)大单体与苯乙烯(St)进行接枝共聚，将得到的双亲性接枝共聚物(PEG—g—PSt)逐步滴加到各种比例的甲醇／水的混合溶剂中，通过该聚合物在混合溶剂中的自组装，制得了PEG—g—PSt微球。用透射电子显微镜(TEM)和激光光散射(LLS)对微球的形态和粒径进行了表征。实验结果表明，改变接枝液组成、接枝液浓度、滴加速度以及混合溶剂组成等反应条件可有效地控制所得微球的粒径及其分布。     

Ni12P5微球的溶剂热合成与表征

以硫酸镍(NiSO4.7H2O)作为镍源,以乙二醇和水作为混合溶剂,利用溶剂热法成功地制备了磷化镍(Ni12P5)微球。X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电镜(TEM)和高分辨透射电镜(HRTEM)等分别对所制备样品进行了表征。结果表明,所得产物为纯的四方相磷化镍(Ni12P5)微球,粒径约为2～5μm;研究了不同实验参数对样品尺寸、形貌及微球形成过程等的影响。最后对磷化镍微球的发光性进行了研究。     

超临界CO2抗溶剂法制备聚乳酸药物缓释微球

以L-聚乳酸为模型体系,超临界CO2为抗溶剂,采用超临界流体抗溶剂法制备聚乳酸微球.考察了压力、温度、溶液浓度、溶液流速、二氯甲烷-丙酮混合溶剂、聚合物分子量等参数对制备微球的形态、粒径及其分布的影响.结果表明,改变工艺参数,可在一定范围内调控微球粒径,所制微球平均粒径0.67～6.64μm,溶液浓度及其流速为主要影响因素;实验条件一定时,采用二氯甲烷-丙酮混合溶剂及强制分散溶液法制备得较小粒径微球.释放度实验结果表明,微球按一级释放方程释药,具缓释效果.     

注凝工艺制备二氧化锆陶瓷微球

采用注凝工艺制备二氧化锆陶瓷微球，测试了微球的性能，研究了分散剂、引发剂以及真空除泡等对浆料性质的影响。结果表明：将催化剂加入至二甲基硅油中可以避免浆料提前固化，有效延长其稳定存放时间，同时还可将浆料固化所需温度从90℃降低到50℃。采用振动分散技术可以获得尺寸分布均匀的二氧化锆陶瓷微球。     

纳米TiO2微球的制备及光催化性能研究

以钛酸四丁酯为前驱体,在油酸和正己烷的混合溶剂中,采用溶剂热技术成功地合成了纳米TiO2微球.以X射线衍射(XRD)、透射电镜(TEM)等方法对产物进行了表征,并对其光催化降解甲基橙溶液的性能进行了研究.实验结果表明:纳米TiO2微球的平均尺寸约为60nm,其中含有粒径平均约4.5nm的超细粒子.此种结构趋向于高的比表面积,与P-25型光催化剂相比,两者对甲基橙溶液的脱色具有相近的光催化活性.     

超临界流体技术制备5-氟尿嘧啶-吲哚美辛-聚乳酸缓释微球

为了考察药物5-氟尿嘧啶(5-Fu)与吲哚美辛(IDMC)的协同作用, 采用超临界流体强制分散溶液技术(SEDS), 以二氯甲烷/二甲亚砜为共溶剂, 制备了复合5-Fu和IDMC的L-聚乳酸(PLLA)微球。利用单因素法探索了制备复合微球的最佳外部条件, 通过表面形貌、 载药量、 粒径分布、 释放性能的检测和体外细胞实验来表征微球的各项性能。结果表明: 当共溶剂二氯甲烷/二甲亚砜比例为30∶1时, 制备该微球的优化条件为39℃、 14MPa; 微球形貌呈类球形, 粒径分布在0.5~5μm; 复合IDMC后微球具有更优良的缓释效果; 载药微球对A549细胞系增殖有明显的抑制作用, 但与复合IDMC前后微球共培养的2组细胞的相对生长速率(RGR)无显著性差异。      

花状CdO微球的制备及其对高氯酸铵热分解的催化性能

采用溶剂热合成-热分解两步法制得花状CdO微球。以醋酸镉为原料、甲醇为溶剂,采用溶剂热法合成由纳米片自组装而成的花状前驱体微球。将前驱体焙烧后,得到形貌保持良好的花状多孔CdO微球。利用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、热重(TG)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和N_2吸附-脱附等手段对样品的物相、化学组成、形貌及孔结构进行表征。借助差示扫描量热(DSC)技术对CdO花状微球催化高氯酸铵(AP)热分解的性能进行评价。结果表明:花状CdO微球对AP热分解过程具有一定的催化作用。添加质量分数为2%的CdO可使AP的高温分解峰值温度从444.4℃降低至402.8℃,分解热从586.9 J/g提高到1091.7 J/g,分解活化能从280.5 kJ/mol减小至83.78 kJ/mol。基于实验结果,提出了CdO花状微球催化AP热分解的可能机理。     

微波辐射分散聚合制备单分散聚甲基丙烯酸甲酯微球

在微波辐射下,以乙醇/水混合溶剂为分散介质,聚乙烯吡咯烷酮为稳定剂,进行了甲基丙烯酸甲酯的分散聚合。利用透射电镜(TEM)、动态激光光散射粒度仪(PCS)研究了微球的形态和粒径大小,探讨了介质中乙醇含量、聚合前期微波功率、引发剂和稳定剂浓度对微球粒径及分布的影响。结果表明,当介质中乙醇质量分数在40%～50%时能得到稳定的聚合物微球。在一定范围内,随着反应前期微波功率的增大,微球粒径增大,粒径分布先减小后变大。与常规加热聚合相比,微波辐射能加快反应速率,提高单体转化率,所得的聚合物微球粒径小,单分散性更好。     

基于水滴模板法直接致技术制备"高尔夫球"型多孔聚苯乙烯微球

介绍了一种基于传统水滴模板法的新型表面图案化致孔技术,并利用这一技术成功在微米尺寸聚合物球形粒子表面实现多孔结构的制备。这种直接致孔技术通过对传统水滴模板法实施方法的改造,成功实现了在微观尺寸三维结构表面的致孔。首先通过微流道法制备得到尺寸均一的微米级聚苯乙烯(PS)微球;之后在高湿度条件下,对聚苯乙烯(PS)微球进行溶剂的直接致孔处理,得到表面具有多孔结构的"高尔夫球"型聚苯乙烯(PS)微球;并进一步通过对溶剂种类、溶剂用量以及湿度的调控,对实现微球致孔的条件进行了讨论。基于这一溶剂直接致孔实施方法的建立,在水滴模板法实施对象的几何造型局限性上进行了突破。     

两步沉淀聚合法制备表面具有羧基的核-壳微球

以高交联的聚二乙烯基苯-55(poly(DVB-55))为核,甲苯/乙腈(体积比1∶3)混合溶剂,采用两步沉淀聚合法,在核的表面接枝了具有羧基官能团的较低交联度的壳,得到了单分散或窄分散微米尺度的poly(DVB55)/poly(DVB55-co-methacrylic acid)核-壳微球。结果表明,以甲苯/乙腈混合物替代纯乙腈作为反应介质可以获得比表面积、孔容、接枝量和粒径相对较大的核-壳微球;随着poly(DVB-55)核的用量的增加或反应时间的缩短或单体和交联剂投料浓度的减小,所得的核-壳微球的粒径减小、接枝量降低、粘连程度减小,微球的均匀性则升高。     

Synthesis of hollow ZrO2 mesopores microspheres with strong adsorption capability by the yeast bio-template route

In this work, cage-like ZrO2 and hollow ZrO2 microspheres with high surface area and strong adsorption capability were successfully synthesized by microwave- ethanol-thermal method using yeasts as bio-template. XRD, SEM, EDS and BET were used to characterize the products. The results show that these micropheres have a size of about 2-3 microm and are composed by ZrO2 particles of 30-40 nm. The maximum specific surface area of them can reach to 384.780 m2/g and there are presences of the inhomogeneous mesopores. Moreover, the template can be removed and tetragonal phase ZrO2 can be obtained without using calcinations, which greatly simplifies the experimental procedure. We also studied the adsorption capability of cage-like ZrO2 and hollow ZrO2 microspheres to methyl orange, the highest adsorption percent was up to 99.5%. The adsorption isotherm conforms to Freundlich equation.     

Environmentally friendly aqueous solution synthesis of hierarchical CaWO4 microspheres at room temperature

An environmentally friendly route for the synthesis of hierarchical CaWO4 microspheres with novel morphology at room temperature has been successfully developed. CaCl2 and Na2WO4 were used as reaction regents, and distilled water was used as an environmentally friendly solvent. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence spectroscopy. This green wet-chemical route provides a simple, one-step, low-cost approach for the large-scale synthesis of hierarchical CaWO4 microspheres with relatively uniform diameters of 3-6 microm. The hierarchical microspheres are built up with numerous nanorods with an average diameter of 50 nm, which are radially oriented to the microsphere center. SEM observations of different intermediates indicate the possible growth process, in which the hierarchical structure growth is from nuclei through kayak-like, rod-like, peanut-like, dumbbell-like, and peach-like structures to final microspheres, via "self-assembled preferential end growth" of kayak-like particles in aqueous solution. The hierarchical CaWO4 microspheres exhibit a strong, broad blue emission peak of 412 nm.     

Synthesis of flower-like CuS nanostructured microspheres using poly(ethylene glycol) 200 as solvent

CuS flower-like microspheres with the diameter of about 3-4 microm constructed by nanoflakes with thickness of about 30-40 nm have been successfully synthesized by a simple wet chemical method. In this reaction system, Poly(ethylene glycol) 200 (PEG 200) was used as solvent, CuCl2 2H2O as cuprum source, and thioacetamide (TAA) as sulfur source. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) in detail. The XRD patterns revealed that the products were pure hexagonal phase of CuS. Experiments with various parameters indicated that the reaction temperature and molar ratio of CuCl2 2H2O to thioacetamide had strong effects on the sizes and morphologies of CuS crystals. A possible growth mechanism on the formation of CuS microspheres was proposed. The PEG 200 acted as solvent, complexing agent, and soft template in this synthesis. Furthermore, optical studies of the products including UV-Vis absorption spectrum and photoluminescence spectrum have also been carried out.     

PVDF/ZrO2杂化膜结构与过滤性能研究

将纳米氧化锆（ZrO2）粒子添加到聚偏氟乙烯（PVDF）膜铸液中,通过相转化法制备了一系列不同ZrO2含量的ZrO2/PVDF杂化膜。通过SEM、EDX、XRD等技术对杂化膜结构进行表征,发现ZrO2粒子填充到聚合物网络结构中,使膜孔径变小,并且降低了膜的结晶度。膜超滤实验表明,随着ZrO2含量的增加,膜纯水通量先增加后减小;膜对牛血清蛋白（BSA）的截留率逐渐增加,而通量衰减有所降低,说明ZrO2的加入能够有效提高膜对BSA的抗污染性能。     

Preparation of CuInS2 microspheres via a facile solution-chemical method

With a mixed solvent of triethylenetetramine-ethylene glycol (1:1, v/v), CuInS₂ microspheres were synthesized by a facile solution-chemical method under the open-air condition. Morphology, structure, phase constituents and optical properties of the as-prepared CuInS₂ powders were characterized by X-ray diffraction (XRD), Energy Dispersive Spectrometer (EDS), scanning electron microscope (SEM) and ultraviolet-visible (UV-vis) spectrophotometry. The characterizations showed that the synthesized CuInS₂ powders had single phase, good crystallinity and stoichiometric composition. Moreover, the prepared CuInS₂ powders showed microspheres with the size from 200 to 400 nm, and their energy band gaps were 1.52 eV, which made them promising candidates as absorber materials for photovoltaic applications.     

单分散介孔氧化硅微球的粒径可控制备

在中性醇-水体系中,采用月桂胺(DDA)为导向剂,通过调整反应物组分的剂量比,研究了具有蠕虫状介孔的单分散氧化硅微球粒径可调控行为。实验表明,当月桂胺与正硅酸乙酯的摩尔比为0.4,正硅酸乙酯的浓度范围在0.138~0.248mol/L之间,改变水/醇比例,可以实现微球粒径在50nm~1μm之间的调控。该方法简单易行,制备得到的微球尺寸均匀,单分散性好,BJH孔径在1.4nm左右。粒径可控的单分散介孔氧化硅微球,通过表面有机化修饰,可以成为改变流体流变行为的优秀添加介质。     

One-pot synthesis of porous hematite hollow microspheres and their application in water treatment

Alpha-Fe2O3 hollow micospheres have been successfully synthesized by solvothermal method at 200 degrees C. The synthesized products are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and the nitrogen adsorption-desorption isotherm technique. The alpha-Fe2O3 hollow microspheres have an average diameter of 2-3 microm, the shell consists of numerous aligned nanorods with length of about 200-400 nm. The effects of solvent and reaction time have been studied. The Ostwald ripening mechanism is proposed to account for the formation of alpha-Fe2O3 hollow microspheres. Because of the porous hollow microstructure and large specific surface area, the microspheres were found to be effective sorbents for the removal of Cr(VI) ions from wastewater.     

Al_2O_3-TiO_2-ZrO_2含纳米结构等离子喷涂层的显微硬度及韧性

为了提高传统Al_2O_3+40%TiO_2等离子喷涂层的力学性能,将纳米结构的ZrO_2粉末引入热喷涂层,采用液相喷雾造粒的方法将纳米ZrO_2-准微米级Al_2O_3/TiO_2颗粒团聚成适用于等离子喷涂的微米级粉体,并用等离子喷涂技术制备出含有纳米结构的陶瓷涂层.利用X射线衍射仪、扫描电镜和显微硬度计等对涂层的微观结构和性能进行了检测.结果表明,最佳喷涂功率40 kW下制备的纳米陶瓷涂层的显微硬度和韧性比传统涂层有了明显提高.     

Development of Hollow Microspheres as Floating Controlled-Release Systems for Cardiovascular Drugs: Preparation and Release Characteristics

Hollow microspheres of cellulose acetate loaded with four cardiovascular drugs (nifedipine [NFD], nicardapine hydrochloride [NCD], verapamil hydrochloride [VRP], and dipyridamole [DIP]) were prepared by a novel solvent diffusion-evaporation method. The oil-in-water emulsion prepared in an aqueous solution of 0.05% poly(vinyl alcohol) medium with ethyl acetate, a water-soluble and less toxic solvent, was used as the dispersing solvent. The yield of the microspheres was up to 80%. The microspheres had smooth surfaces, with free-flowing and good-packing properties. Scanning electron microscopy (SEM) confirmed their hollow structures, with sizes in the range 489–350 μm. The microspheres tended to float over the gastric media for more than 12 h. The drug loaded in hollow microspheres was in an amorphous state, as confirmed by differential scanning microscopy (DSC). The release of the drugs was controlled for more than 8 h. The release kinetics followed different transport mechanisms depending on the nature of the drug molecules.