热处理温度对蛋白石晶体的影响

 采用等体积快速混合法制备了不同粒径的单分散SiO₂微球,通过重力垂直沉降自组装形成了蛋白石模板,研究了热处理温度对蛋白石晶体模板形貌、结构与光学性能的影响。SEM,TG-DSC,UV-Vis等分析表明：热处理可提高组装微球的粘合性与模板的机械强度;SiO₂胶体模板煅烧温度在700～800 ℃较为合适;热处理能够改变蛋白石晶体光子带隙的位置,随着煅烧温度的升高,带隙发生蓝移并且带隙逐渐变窄。     

Preparation of uniform porous hydroxyapatite biomaterials by a new method

In this paper, a new method of preparation of uniform porous hydroxyapatite biomaterials was reported. In order to obtain uniform porous biomaterials, disk samples were formed by the mixture of hydroxyapatite (HAP) powders and monodispersed polystyrene microspheres, and then HAP uniform porous materials with different diameter and different porosity (diameter: 436 ± 25 nm, 892 ± 20 nm and 1890 ± 20 nm, porosity: 46.5%, 41.3% and 34.7%, respectively) were prepared by sintering these disk samples at 1250 °C for 5 h. The pure phase of HAP powders fabricated by the hydrothermal technology was confirmed by X-ray diffraction (XRD). The surface and size distribution of pores in HAP biomaterials were observed by scanning electron microscopy (SEM), and the pore size distribution in porous HAP biomaterials was tested by mercury intrusion method.     

磁微球及其在生化分离分析中的应用

磁微球是以金属或金属氧化物为核,外面包被带有活性基团物质的一种新型生物分离材料。目前制备磁微球的方法有包埋法、聚合法、浸渍法、挤压法和生物合成法等。这种微球通过其活性基团与化学、生化和生物物质连接后,利用其顺磁性外加一定磁场可实现与介质分离。本文全面地介绍了磁微球的制备,详尽评述了其在免疫分析、核酸杂交分析、基因测序、细胞分离、酶的固定、受体分离等各个领域的应用。     

Crosslinked Polyacrolein Microspheres with High Loading of Aldehyde Groups for Use as Scavenger Resins in Organic Synthesis

Summary: Suspension polymerization yielded microspheres (40–50 μm) of polyacrolein. Smooth and rugged surfaces can be created by varying the polymerization procedure. We have shown that the polyacrolein resins with a high loading of aldehyde groups serve as effective scavengers for primary amines and may be used to remove compounds bearing amino groups in the combinatorial synthesis of compound libraries. Copolymerization with styrene can help to separate the adjacent aldehyde groups, thus making the functional groups more available in organic reactions. The polyacrolein resins in the aldehyde form or after appropriate chemical modifications may also be useful as support materials in solid‐phase synthesis.

The SEM image of macroporous polyacrolein microspheres with toluene as porogen prepared by free radical polymerization.     

High-throughput generation of uniform droplets from parallel microchannel droplet generators and the preparation of polystyrene microsphere material

To prepare uniform polystyrene particles with ten microns of diameter, a parallel scaling-up strategy for the capillary-assembled stepwise microchannel was developed, which created uniform droplets with high-throughput and formed a large amount of emulsion templates for the polymerization of styrene and cross-linker. The microchannel droplet generator was robust for the flow rate deviation of the continuous phase in the jetting flow, and droplet generation frequency up to 2.8 × 10⁴ Hz was achieved with only four parallel droplet generators, which were much more efficient than the parallelly scaled microfluidic devices working in dripping flow. 32–52 μm average diameter droplets with 4.5%–8.4% diameter variation coefficients were successfully prepared from the microchannel device fabricated by low-cost 3D-print method, and the droplets were subsequently turned to solid particles via a two-step polymerization in the platform. The polystyrene particles were further reduced to 16.9–23.5 μm with 5.0%–8.6% diameter variation coefficients due to the accompanying emulsion polymerization, and the working capacity of the platform reached hundred milligrams of particles per hour.     

Formation of highly monodispersed emulsifier-free cationic poly(methylstyrene) latex particles

Highly monodispersed emulsifier-free poly(methylstyrene) (PMS) latex particles were prepared via an emulsifier-free emulsion polymerization in the presence of 2,2′-azobis-(2-amidineopropane) dihydrochloride (V-50) as an initiator. A combination of kinetics and molecular weight distribution studies revealed that the polymerization followed the micellization nucleation mechanism. Results showed that an appropriate initiator concentration was necessary to obtain monodisperse and stable latex particles. Conversion of methylstyrene was found to increase significantly with increasing initiator concentrations. However, the size of PMS latex particles decreased with both the increase of initiator concentration and the reaction temperature at a constant ionic strength. The particle size was increased as the ionic strength of the aqueous phase increased, yet the variation of ionic strength had little effect on the particle size distribution. SEM micrographs showed that an agitation rate of 350 rpm or higher was required in order to produce highly monodispersed poly(methylstyrene) latex particles. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2069–2074, 1999     

Synthesis of divinylbenzene–maleic anhydride microspheres using precipitation polymerization

Narrow disperse micron-range divinylbenzene-maleic anhydride microspheres have been prepared in near quantitative yields using precipitation polymerization. A variety of solvents were investigated for use as the reaction medium with a 40:60 mixture of methyl ethyl ketone and heptane providing the best results. The effects of solvent composition on particle size and morphology and monomer loading effects were also investigated. Particle size decreased with increasing solvency (increasing MEK fraction) while increases in monomer loading caused larger particle sizes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2223–2227, 1998     

悬浮液气-液界面二元胶体颗粒的漂浮组装机理

提出一种在悬浮液气-液界面漂浮组装亚微米单分散聚苯乙烯(PS)微球和纳米SiO2颗粒二元胶粒晶体的新方法, 并系统研究了漂浮组装机理. 研究表明, 聚苯乙烯微球和二氧化硅两种胶体颗粒在悬浮液气-液界面的漂浮组装是以PS微球的组装为主导的. 在一定PS微球相浓度范围内, 悬浮液中PS 微球与SiO2颗粒的初始体积配比基本不影响PS微球有序组装的形成. PS微球粒径在150-500 nm时易于形成有序排列, 较小或较大粒径的PS微球难以形成有序排列. SiO2颗粒的组装是一种以PS微球为“基底”的沉积过程. 二元胶粒晶体中SiO2颗粒的体积分数由其在混合悬浮液中的相浓度所决定.     

Metal Emulsion-Based Synthesis,Characterization, and Properties of Sn-Based Microsphere Phase Change Materials

A comparative study of the metal emulsion-based synthesis of Sn-based materials in two different types of molten salts (namely LiCl–KCl–CsCl and LiNO₃-NaNO₃-KNO₃ eutectics) is presented, and the properties of Sn, Sn-Cu and Sn-Cu-Zn microsphere phase change materials prepared in chloride salts are evaluated by differential scanning calorimetry (DSC) to understand the effect of element doping. Despite a high ultrasonic power (e.g., 600 W or above) being required for dispersing liquid Sn in the chloride system, well-shaped Sn microspheres with a relatively narrow size range, e.g., about 1 to 15 µm or several micrometers to around 30 µm, can be prepared by adjusting the ultrasonic power (840–1080 W), sonication time (5–10 min) and the volume ratio of salts to metal (25:1–200:1). Such a method can be extended to the synthesis of Sn-based alloy microspheres, e.g., Sn-Cu and Sn-Cu-Zn microspheres. In the nitrate system, however, a very low ultrasonic power (e.g., 12 W) can be used to disperse liquid Sn, and the particles obtained are much smaller. At low ultrasonic power (e.g., 12 W), the particle size is generally less than 10 or 4 µm when the sonication time reaches 2 or 5 min, and at high ultrasonic power, it is typically in the range of hundreds of nanometers to 2 µm, regardless of the change in ultrasonic power (480–1080 W), irradiation time (5–10 min), or volume ratio of salts to metal (25:1–1000:1). In addition, the appearance of a SnO phase in the products prepared under different conditions hints at the occurrence of a reaction between Sn droplets and O₂ in situ generated by the ultrasound-induced decomposition of nitrates, and such an interfacial reaction is believed to be responsible for these differences observed in two different molten salt systems. A DSC study of Sn, Sn-Cu, and Sn-Cu-Zn microspheres encapsulated in SiO₂ reveals that Cu (0.3–0.9 wt.%) or Cu-Zn (0.9 wt.% Cu and 0.6% Zn) doping can raise the onset freezing temperature and thus suppress the undercooling of Sn, but a broad freezing peak observed in these doped microspheres, along with a still much higher undercooling compared to those of reported Sn-Cu or Sn-Cu-Zn solders, suggests the existence of a size effect, and that a low temperature is still needed for totally releasing latent heat. Since the chloride salts can be recycled by means of the evaporation of water and are stable at high temperature, our results indicate that the LiCl–KCl–CsCl salt-based metal emulsion method might also serve as an environmentally friendly method for the synthesis of other metals and their alloy microspheres.     

Preparation of HNS microspheres by rapid membrane emulsification

In order to improve the dispersibility and loading efficiency of 2,2′,4,4′,6,6′-hexanitrostilbene (HNS), HNS microspheres were prepared by rapid membrane emulsification method with nitrocellulose (NC) as binder. The effects of NC solution concentration, stirring speed and polyvinyl alcohol (PVA) solution concentration on microspheres were investigated. It was characterized by scanning electron microscope (SEM), X-ray diffractometer (XRD), differential thermal analysis (DTA) and angle of repose analyzer. The results show that the HNS microspheres prepared with 5 wt% NC solution concentration, stirring speed of 100 rpm and 2 wt% PVA solution concentration have better regular morphology, higher sphericity, unchanged crystalline shape, increased activation energy and significantly improved dispersibility compared with the refined HNS. Rapid membrane emulsification has a series of advantages such as green, low cost and easy scale up, which provides a better way to prepare microspheres of energy materials.