Preparation of Sustained-release Silybin Microspheres by Spherical Crystallization Technique

Aim To improve the dissolution rate and bioavailability of silybin. Methods Sustained-release silybin microspheres were prepared by the spherical crystallization technique with soliddispersing and release-retarding polymers. A differential scanning calorimeter and an X-ray diffractometer were used to investigate the dispersion state of silybin in the microspheres. The shape, surface morphology, and internal structure of the microspheres were observed using a scanning electron microscope. Characterization of the microspheres, such as average diameter, size distribution and bulk density of the microspheres was investigated. Results The particle size of the microspheres was determined mainly by the agitation speed. The dissolution rate of silybin from microspheres was enhanced by increasing the amount of the dispersing agents, and sustained by the retarding agents. The release rate of microspheres was controlled by adjusting the combination ratio of the dispersing agents to the retarding agents. The resuits of X-ray diffraction and differential scanning calorimetry analysis indicated that silybin was highly dispersed in the microspheres in amorphous state. The release profiles and content did not change after a three-month accelerated stability test at 40 ℃ and 75% relative humidity. Conclusion Sustained-release silybin microspheres with a solid dispersion structure were prepared successfully in one step by a spherical crystallization technique combined with solid dispersion technique. The preparation process is simple, reproducible and inexpensive. The method is efficient for designing sustained-release microspheres with water-insoluble drugs.

Fabrication of ZIF-8 membranes on dual-layer ZnO-PES/PES organic hollow fibers by in-situ crystallization

Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membrane layer, which usually requires complex surface modification or seeding. Herein, we demonstrate that a dual-layer asymmetric polymer support prepared by a simple spinning process is a good candidate for the preparation of ZIF-8 membrane. The inner layer of the support is an organic hollow fiber(PES) with finger-like pores, and the outer layer is a ZnO-PES composite layer with finger-like pores also. The ZnO-PES composite layer is expected to contain uniform ZnO crystals in the polymer matrix, i.e., the ZnO particles in the skin layer of the support are not easy to fall off. Under the induction of ZnO particles in the outer layers, continuous ZIF-8 membranes can be prepared by single in-situ crystallization, showing good adhesion to the supports. The obtained ZIF-8 membranes show a H_(2) permeance of 8.7 × 10^(-8)mol·m^(-2)·s^(-1)·Pa^(-1) with a H_(2)/N_(2) ideal separation selectivity of 18.0. The design and preparation of this dual-layer polymer support is expected to promote the large-scale application of MOF membranes on polymer supports.

Research on properties of hollow glass microspheres/epoxy resin composites applied in deep rock in-situ temperature-preserved coring

Deep petroleum resources are in a high-temperature environment.However,the traditional deep rock coring method has no temperature preserved measures and ignores the effect of temperature on rock porosity and permeability,which will lead to the distortion of the petroleum resources reserves assessment.Therefore,the hollow glass microspheres/epoxy resin(HGM/EP)composites were innovatively proposed as temperature preserved materials for in-situ temperature-preserved coring(ITP-Coring),and the physical,mechanical,and temperature preserved properties were evaluated.The results indicated that:As the HGM content increased,the density and mechanical properties of the composites gradually decreased,while the water absorption was deficient without hydrostatic pressure.For composites with 50 vol%HGM,when the hydrostatic pressure reached 60 MPa,the water absorption was above 30.19%,and the physical and mechanical properties of composites were weakened.When the hydrostatic pressure was lower than 40 MPa,the mechanical properties and thermal conductivity of composites were almost unchanged.Therefore,the composites with 50 vol%HGM can be used for ITPCoring operations in deep environments with the highest hydrostatic pressure of 40 MPa.Finally,to further understand the temperature preserved performance of composites in practical applications,the temperature preserved properties were measured.An unsteady-state heat transfer model was established based on the test results,then the theoretical change of the core temperature during the coring process was obtained.The above tests results can provide a research basis for deep rock in-situ temperature preserved corer and support accurate assessment of deep petroleum reserves.

Probing the Nucleation and Growth Kinetics of Bismuth Nanoparticles via In-situ Transmission Electron Microscopy

The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of intermediate state structure during nucleation and growth.In this work,the evolution process of bismuth nanoparticles induced by electron beam was revealed by in-situ transmission electron microscopy(TEM)at atomic scale.The experimental results demonstrate that the size,stable surface and crystallographic defect have important influences on the growth of Bi nanoparticles.Two non-classical growth paths including single crystal growth and polycrystalline combined growth,as well as,corresponding layer-by-layer growth mechanism along{012}stable crystal plane of Bi nanoparticles with dodecahedron structure were revealed by in-situ TEM directly.These results provide important guidance and a new approach for in-depth understanding of the nucleation and growth kinetics of nanoparticles.

Crystal phase control and ignition properties of HNS/CL-20 composite microspheres prepared by microfluidics combined with emulsification techniques

Improved controllability and energy density of ignition agents are of great significance for the devel-opment of energetic composite materials.In this study,droplet microfluidics and emulsification tech-niques were combined to prepare HNS/CL-20 composite microspheres with polyglycidyl azide polymer(GAP)as the binder.The influence of binder content on the morphology of microspheres was investi-gated,and the microspheres were characterized and tested for particle size,crystal structure,thermal decomposition,dispersibility,mechanical sensitivity,combustion behavior and detonation performance.The results showed that microspheres prepared with a binder content of 3%had higher sphericity and particle size uniformity.The microspheres retained the crystal structure of both HNS and CL-20(ε-type).Compared with raw HNS,the microspheres had higher apparent activation energy,better safety per-formance,and good dispersibility.The ignition experiments and detonation performance tests show that HNS/CL-20 composite microspheres have excellent ignition performance,obvious combustion flame,and significant energy release effects,which are expected to achieve high energy and high-speed response of the igniter,thus improving the ignition reliability in special environments or systems.

Crystalline Morphology and Crystallization Characteristics of In-situ Blends of Anionic Polyamide 6 with Noncrystallizable Semiaromatic Polyamide Copolymer

A noncrystallizable semiaromatic polyamide copolymer（NSAP） was dissolved in molten caprolactam, and PA6/ NSAP blends were produced in-situ via the anionic ring-opening polymerization of caprolactam. The presence of a single loss tangent（tanS） peak measured by means of dynamic mechanical analysis（DMA） proves the miscibility between PA6 and NSAP in the blends. It was found that there existed drastic changes in the crystallographic form and crystallization kinetics for the in-situ blends, e.g. , when 20% NSAP was added, nearly all crystallites existed in the ,y form and the crystallization could hardly occur upon cooling even at a rate of 2.5 ℃/min. Moreover, cold crystallization appears during the subsequent heating, and its melting point is 40 ℃ lower than that of the virgin system. On the other hand, the size of the spherulites only decreases modestly. It is suggested that the introduction of irregular stiff segments originated from NSAP into PA6 macromolecule chain, which resulted from transamidation during the polymerization play a dominant role in the drastic change of crystallization kinetics and the resultant morphology of the in-situ blends.

Novel MoS2 Microspheres Formed by Solid-State Assembly of Ultratliin Nanoslieets

The MoS2 microspheres with high specific surface area assembled by ultrathin nanosheets have been successfully synthesized by a facile and environmentally friendly reaction in a closed reactor at moderate temperatures.The solid-state assembly was realized by a simple calcination process,and the annealing temperature played a key role in the formation of the final microspheres.The influences of reaction temperature were carefully investigated.A possible formation mechanism about the solid-state assembly was proposed based on the experimental results.

<i>In-Situ</i>Monitoring of Chemical Vapor Deposition from Trichlorosilane Gas and Monomethylsilane Gas Using Langasite Crystal Microbalance

Using the langasite crystal microbalance (LCM), the trends in film thickness produced by means of the chemical vapor deposition using trichlorosilane gas, monomethylsilane gas and their mixed gas were observed at 600?C and evaluated by comparison with the information from a transmission electron microscope (TEM). The crystalline silicon film thickness from trichlorosilane gas was comparable to that of an amorphous silicon carbide film from monomethylsilane gas. The film obtained from the gas mixture was amorphous and was the thinnest in this study. Because the thickness trend obtained by the LCM agreed with that by the TEM, the LCM is shown to be a convenient evaluation tool for the behavior of various film deposition.

Crystallization Behavior of Palm Kernel Oil Monitored by <i>In-Situ</i>Focused Beam Reflectance Measurement (FBRM) and Particles Video Microscope (PVM) during Suspension Crystallization

Crystallization behavior and kinetics study of palm kernel oil (PKO) were investigated using differential scanning calorimetry (DSC) by controlling cooling and reheating rate within a certain range of temperature. The evolution of morphology and particle counts was analyzed by focused beam reflectance measurement (FBRM) and particles video microscope (PVM) at the nucleation stage during suspension crystallization. The particle counts and morphological evolution from needle-like aggregations to amorphous form from PVM were observed during the initial crystallization stage, which meant that a phase transition was likely to occur. This work can give a better understanding of complicated fat system crystallization behavior and provide some critical instructions to control fractionation process.

喷雾-反溶剂结晶法制备掺杂铝粉的复合微球

纳米铝粉作为高能添加剂广泛应用于含能复合材料领域。然而,制备高球形度铝粉掺杂的复合微球却面临着一系列挑战。采用喷雾与反溶剂结晶相结合的方法,探索了一种制备纳米铝粉与有机分子形成复合功能微球的喷射-结晶途径。通过自主设计的内混三流式空气雾化喷嘴,将前驱液雾化成液滴,反溶剂接收浴接收后,溶剂与反溶剂发生快速的相互扩散和传质过程,含能分子模拟物蔗糖八乙酸酯(SOA)在液滴内部析出,将铝粉包裹在内,洗涤干燥后得到铝粉掺杂的复合微球。通过调控合适的雾化、溶剂与反溶剂、添加剂等条件,成功解决了干燥后复合微球球形度低、微球之间相互团聚等现象,最终制备出粒径分布窄、形貌均一、分散性较好、球形度和密实度较高的掺杂铝粉的微球复合材料。

纳米纤维素嵌合型晶胶微球的多微管成形与模拟

利用多微管反应器,采用结晶致孔与低温聚合方法可实现纳米纤维素嵌合型晶胶微球的规模化制备。该过程中内嵌纳米纤维素的甲基丙烯酸羟乙酯单体溶液经多微管反应器的成形是首要条件,研究其成形过程的动力学特性具有重要意义。利用高速成像和计算流体力学(CFD)模拟方法对不同入口流速(6、8、10 mm·s^(-1))下内嵌不同比例(单体质量的1%、3%、5%)纳米纤维素的甲基丙烯酸羟乙酯液滴形成过程进行可视化研究,考察了纳米纤维素含量对液滴成形、液滴直径分布、颈缩线长度、液滴下落速度等因素的影响规律。结果表明,内嵌纳米纤维素的甲基丙烯酸羟乙酯液滴经多微管反应器的成形及滴落,会经历拉伸与压缩过程,最后稳定为球状,测得液滴直径和颈缩线长度与纤维素浓度呈正相关,纤维素含量的增加使得单体溶液黏度和表面张力系数增加,从而增大液滴尺寸和颈缩线长度,模拟得到的结果与实验基本一致,液滴直径差异为2.1%~6.3%,颈缩线长度差异为7.2%~11.9%;在对液滴成形的放大模拟中,10 mm·s^(-1)的入口流速下液滴平均直径为3.98 mm,平均颈缩线长为4.14 mm。最终,利用多微管反应器成功制备了纳米纤维素嵌合型晶胶微球,微球有效孔隙率可达80%以上,绝干孔隙率接近90%,是生物分离领域与微生物贴壁生长的理想载体。

PS@SiO_(2)微球的合成及其三维光子晶体的光学性能

以乙烯基三乙氧基硅烷为硅源,通过其在碱性条件下的水解缩聚,在聚苯乙烯(PS)微球表面包覆乙烯基修饰的二氧化硅(Vi-SiO_(2))壳层制备PS@SiO_(2)微球,并通过刮涂法进一步制得PS@SiO_(2)三维光子晶体。对比了PS微球在包覆Vi-SiO_(2)前后的微观形貌、粒径和化学组成的差异,分析了PS@SiO_(2)光子晶体的形貌和光学性能。结果表明:Vi-SiO_(2)在PS微球表面形成了均匀且光滑的外壳,并且Vi-SiO_(2)的包覆对PS微球的单分散性和球形度无明显影响。由4种不同粒径的PS@SiO_(2)微球自组装的三维光子晶体都具有规则的面心立方结构,其结构色随PS@SiO_(2)微球粒径的增大发生红移,并且都具有虹彩效应。

工业失效的甲醇制烯烃催化剂微球原位晶化研究

为了解决工业失效的甲醇制烯烃(MTO)催化剂的资源化利用问题,实现MTO催化剂的循环利用,通过原位晶化的方法,以工业失效的MTO催化剂微球为原料,在水热合成体系中成功制备了以SAPO-34分子筛为活性组分的MTO催化剂。利用XRD、SEM、N_(2)吸/脱附、XRF、NH_(3)-TPD和氘代乙腈(CD_(3)CN)红外等表征手段分析了原位晶化前后催化剂的晶体结构、形貌特征、孔道结构、元素组成及酸性等,并采用固定流化床反应器考察了原位晶化前后催化剂在MTO反应中的催化性能(催化剂40.0 g、反应温度480℃、常压、甲醇质量空速4 h^(-1)、原料为纯甲醇)。结果表明,与原位晶化前催化剂相比,原位晶化后催化剂的相对结晶度提高了76%,比表面积增加了1.4倍,B酸活性中心数量增加了1.1倍;在MTO反应中,双烯(乙烯和丙烯)选择性最高达到89.64%,与原位晶化前催化剂相比,双烯选择性提升了3.3%,二甲醚以及C_(4)和C_(5+)等重烃含量(质量分数)明显降低,且原位晶化后催化剂具有优异的稳定性。

SiO_(2)光子晶体的制备及其在增强上转换发光的应用

用改进的St?ber法制备了均一分散的SiO_(2)微球。探讨了不同温度环境和正硅酸乙酯(TEOS)的用量对生成微球粒径大小的影响。用扫描电子显微镜、分光光度计、X射线衍射仪紫外-近红外吸收发射光谱仪等仪器对粉末和薄膜的形貌与光学性能进行表征。结果表明:随着温度的增加,微球的粒径不断减小。TEOS试剂的用量增加,生成微球的粒径也随之增加。讨论了不同温度的自组装环境对光子晶体自组装的影响。结果表明,当自组装温度为55℃时制备的二氧化硅光子晶体薄膜质量最高。用980 nm激发光对旋涂在玻璃基板和光子晶体上的上转换薄膜进行发光测试,红光发光增强1.72倍,绿光发光增强1.93倍。这是由于带隙位于激发光波段的光子晶体表面具有高光子态密度,能够增强发光粒子周围电磁场强度,提高了电子跃迁的几率,从而增强了荧光强度。

Investigation of the Micro-Mechanics of an Extruded Precipitation-Strengthened Magnesium Alloy under Cyclic Loading

Precipitation strengthening is a crucial microscopic mechanism for enhancing the strength of magnesium alloys. In order to elucidate the influence of precipitation on the microscopic deformation mechanisms and macroscopic mechanical response of magnesium alloys under cyclic loading conditions, we employed a crystal plasticity model to analyze the stress-strain curves, specific crystal plane diffraction intensities, and the temporal evolution of various microscopic deformation mechanisms and twinning volume fractions for an extruded magnesium alloy, AXM10304, containing coherent precipitates. The research findings indicate that precipitation does not fundamentally alter the microscopic mechanisms of this alloy. However, it hinders twinning during the compression stage, mildly promotes detwinning during the tension stage, and enhances tension secondary hardening by elevating the difficulty of activation of the prismatic slip.

Growth mechanism of reinforcements in in-situ synthesized (TiB+TiC)/Ti composites

The growth mechanism of reinforcement in in situ synthesized (TiB+TiC)/Ti composites was investigated. The results show that reinforcements nucleate and grow in a way of dissolution precipitation. The morphologies of reinforcements are closely related to the solidification paths and crystal structure of reinforcements. TiB, as a reinforcement, is liable to grow along [010] direction and forms in short fibre shape due to its B27 structure, whereas primary TiC is liable to form composition undercooling and grow in dendritic shape. TiC phases precipitated in binary eutectic and ternary eutectic reactions grow in equiaxial shape. The addition of aluminum element refines TiB and TiC particles, and makes TiC reinforcements grow into the equiaxial particles easily. The addition of graphite adjusts the solidification paths and forms more TiC with dendritic shape. [

Facile Fabrication of Large Area Polystyrene Colloidal Crystal Monolayer via Surfactant-free Langmuir-Blodgett Technique

A facile and novel method for the production of a large area of well-ordered polystyrene （PS） colloidal crystal monolayer was established using the surfactant-free Langmuir-Blodgett （LB） technique. The hydrophobic property （film-forming ability） of PS spheres was improved by a thermo-rheology treatment before LB assembly, and a large film was obtained. In contrast to the traditional LB technique, no surfactant was needed in this method, which could eliminate the additional contamination of surfactants in the preparation process and provided the products with versa- tile applications in nanosphere lithography （NSL） for biosensor, surface plasmon resonance, and surface enhanced Raman spectroscopy .

In-situ observations on interphase boundary migration and grain growth during α/γ phase transformation in iron-4.2%Cr alloy

In-situ observations on α/γ phase transformation were made to study the effects of grain boundary microstructures on the formation of a new phase and the migration of α/γ interphase boundary in an iron4. 2%Cr alloy. It was found that triple junctions with more random boundaries could be the primary nucleation sites for a new phase, while triple junctions with low angle or low ∑ coincidence boundaries did not play any role as preferential sites. The migration of α/γ interphase boundary during heating over the transformation temperature range showed the two stage behaviour characterized by a stage with a migration velocity of 0. 33-0. 75 mm/s and secondly by a stage with 3. 7-7. 6 mm/s. It was also found that abnormal grain growth and a high density of ∑3 coincidence boundaries could occur in a phase with bcc structure after cycling of α/γ phase transformation. A new mechanism of nucleation and growth of a new phase in α/γ phase transformation is proposed on the basis of roles of plane-matching interphase boundaries, as previously discussed on the origin of anisotropy of grain growth due to the migration of {110} plane-matching boundaries in Fe-3z%Si alloy. The most recent theoretical work on the distribution of plane-matching boundaries in solids with different crystal structures was found to be useful for the understanding of nucleation and growth during α/γ phase transformation.

光子晶体结构生色碳纤维/涤纶混纺纱线的制备及其性能

针对碳纤维难着色的问题,提出利用结构生色实现碳纤维/涤纶混纺纱线的着色。以聚(苯乙烯-甲基丙烯酸)胶体微球为结构基元,利用浸渍提拉法在碳纤维/涤纶混纺纱线上构筑光子晶体生色结构。分析组装液质量分数和自组装温度对结构色的影响,探究胶体微球在纱线表面组装成光子晶体的过程,利用聚二甲基硅氧烷(PDMS)封装技术提升结构生色纱线的色彩耐久性。结果表明:当组装液质量分数为70%、自组装温度为40℃时,可以在纱线表面构筑得到结构色明亮的光子晶体;胶体微球在纱线表面的组装过程归纳为预备阶段、堆砌聚集和完备阶段;经PDMS封装后的结构生色纱线经历水洗摩擦后依旧保持原有的色彩鲜艳度。该研究可为实现彩色碳纤维制品的现代化生产和应用提供新的策略。

磁微碳球的制备及其对结晶紫染料的吸附研究

通过水热法制备磁核,酚醛树脂提供碳源,引入硅源作为硬模板,制备得到磁性复合碳球;采用扫描电子显微镜、比表面积及孔隙度分析仪和振动样品磁强计对材料性能进行表征。将所得磁微碳球用于对水溶液中结晶紫染料进行吸附,考察了吸附时间、温度、染料初始浓度对吸附过程的影响,并通过吸附动力学、吸附等温线、吸附热力学对吸附过程机理进行研究分析。结果表明:该材料粒径介于1.5~2μm;具备较为优异的比表面积(526m2/g)和孔容(0.832cm3/g);具有超顺磁性,在外加磁场的作用下可以实现与染料废水的快速分离;吸附动力学符合拟二级动力学模型,吸附等温线符合Langmuir模型,为单分子层吸附;热力学分析表明,该吸附为自发的吸热过程。磁微碳球作为吸附剂可有效地去除染料废水中的结晶紫,解决了吸附剂回收困难的问题,为染料废水治理提供了新的技术方法。