多分散性对嵌段共聚物微观相行为影响的耗散粒子动力学模拟研究进展

嵌段共聚物通过微观相分离形成的各种有序结构在纳米印刷、药物输送、太阳能电池模板制备等领域有着广泛的应用.如何实现这些有序结构的有效调控是大家普遍关心的问题.近期的实验及理论研究表明嵌段长度的多分散性对嵌段共聚物的微观相行为有着不可忽视的影响.本文综述了近年来在AB型两嵌段及ABA型三嵌段共聚物的实验及理论研究中的一些主要进展,重点介绍了基于耗散粒子动力学的模拟研究进展.并对多分散性可能带来潜在重要影响的嵌段共聚物相关体系的未来发展方向进行了展望.     

聚(γ-苄基-L-谷氨酸)-b-聚(γ-十二烷基-L-谷氨酸)二嵌段共聚物的合成与表征

合成一种分子量分布窄、两嵌段侧链不同的新型聚(γ-苄基-L-谷氨酸)和聚(γ-十二烷基-L-谷氨酸)的二嵌段聚肽(poly(γ-benzyl-L-glutamate)-b-poly(γ-dodecyl-L-glutamate),PBLG-b-PDLG),并研究该嵌段聚肽的分子结构、热性能及液晶性.PBLG-b-PDLG的合成是利用N-羧酸内酸酐(N-carbonyl anhydride,NCA)法,以正己胺为引发剂,在0℃的条件下的氯仿溶液中,先将γ-苄基-L-谷氨酸NCA开环聚合获得了末端带胺基的活性PBLG-NH2沉淀后,再以其为引发剂加入γ-十二烷基-L-谷氨酸的NCA继续反应.氢核磁共振波谱(1H-NMR)和凝胶渗透色谱(GPC)用于表征两嵌段的摩尔比、分子量及其分布,发现嵌段聚肽的分子量分布只有1.07～1.09.由红外光谱(IR)的分析得知PBLG-b-PDLG的二次结构为刚直棒状的α-螺旋结构.利用示差扫描量热分析法(DSC)考察材料的热性质,发现不同组成的PBLG-b-PDLG有不同的热行为,而在100℃附近都出现了微弱的热致相转变.采用偏光显微镜观察PBLG-b-PDLG磁场取向膜的相变行为中发现其相结构不同于一般无规共聚物所呈现的胆甾液晶结构,同时用在PBLG-b-PDLG的二氯乙烷溶致液晶溶液中观察到一般近晶相所呈现的扇形织构.     

Preparation of porous silica spheres with self-dispersing properties

A sol-gel procedure in a water/oil emulsion was introduced for the synthesis of porous silica spheres. Tetraethoxysilane was used as the silica source. The specific surface area and total pore volume of the product reached 772.3 m2/g and 0.663 cm3/g, respectively. The electrolyte washing process conferred a surface charge to the product, which displayed self-dispersal properties in water. The porous spheres have potential applications in the fields of drug delivery, controlled release capsules, indoor air pollutant scavengers, and hydrogen storage agents. The oil phase, which accounts for over 8O% of the chemical cost of the procedure, could largely be recycled by filtering, standing, and layering. The whole procedure is suitable for application as an industrial process.     

磷钨酸/碳纳米管/TiO2复合纳米材料制备及光催化性能研究

采用溶胶凝胶法制备了磷钨酸(HPW)/碳纳米管(CNTs)/TiO2复合纳米颗粒,利用X-射线衍射、BET低温氮吸附、红外光谱、透射电子显微镜及紫外-可见漫反射光谱等对其进行了性能表征.实验结果表明,在HPW与CNTs的共同作用下,使CNTs在前驱体溶剂体系中的分散性得到有效改善,更利于TiO2在其表面的均匀分布,提高了TiO2的光利用率,从而使TiO2复合纳米材料的光催化性能得到明显改善.     

陶瓷干法造粒过程坯料颗粒成形与雾化液含量的影响

为研究陶瓷干法造粒制粉过程坯料颗粒成形与雾化液含量的关系,基于欧拉-欧拉双流体模型模拟干法造粒制粉过程坯料颗粒与雾化液混合过程,同时对坯料颗粒流动性、颗粒级配及粗糙度进行实验分析,验证数值模拟结果正确性.仿真结果表明:当雾化液含量分别为100 mL、200 mL、300 mL时,坯料颗粒在造粒室内的分散性无明显差异,团聚现象不明显;当雾化液含量分别为400 mL、500 mL时,坯料颗粒在造粒室内的分散性有明显变化,团聚现象显著.实验结果表明:当雾化液含量分别为100 mL、200 mL、300 mL、400 mL、500 mL时,坯料颗粒的流动性指数依次为63.5;、83.0;、90.0;、77.0;、61.0;,有效坯料颗粒百分比依次为72;、83;、90;、82;、65;,粗糙度系数平均值依次为1.38、1.43、1.26、1.49、1.57.综合分析说明:数值仿真与实验结果基本相吻合,造粒过程中雾化液含量为300 mL时,干法造粒制粉过程造粒室内坯料颗粒的分散性较好,且基本无团聚现象;坯料颗粒的流动性最佳、颗粒级配最均匀、粗糙度整体最优,即造粒效果最好.     

Circulation intensity and axial dispersion of non-cohesive solid particles in a V-blender via DEM simulation

In this study, discrete element method （DEM） was employed to simulate the movement of non-cohesive mono-dispersed particles in a V-blender along with particle-particle and particle-boundary interactions. To validate the model, DEM results were successfully compared to positron emission particle tracking （PEPT） data reported in literature. The validated model was then utilized to explore the effects of rotational speed and fill level on circulation intensity and axial dispersion coefficient of non-cohesive particles in the V-blender. The results showed that the circulation intensity increased with an increase in the rotational speed from 15 to 60 rpm. As the fill level increased from 20% to 46%, the circulation intensity decreased, reached its minimum value at a fill level of 34% for all rotational speeds, and did not change significantly at fill levels greater than 34%. The DEM results also revealed that the axial dispersion coefficient of particles in the V-blender was a linear function of the rotational speed. These trends were in good agreement with the experimentallv determined values reported bv previous researchers.     

磁性复合流体分散性及其对BK 7光学玻璃抛光性能的影响

针对BK7光学玻璃材料去除率和抛光质量不断提高的需求,提出通过减少磁性复合流体(MCF)抛光液颗粒的团聚、提高MCF分散性,配制性能优良的抛光液,提高BK7光学玻璃的MCF抛光性能.MCF中添加不同质量分数的高分子类分散剂聚乙烯醇(PVA),采用激光粒度分布仪测试MCF抛光液中颗粒的粒径分布和中位粒径,探究不同PVA浓度的抛光液对BK7光学玻璃抛光性能的影响.试验结果表明:当PVA质量分数为3%时,中位粒径达到最小值5.854μm,MCF的分散性最好,对光学玻璃的抛光性能大幅提高,当PVA质量分数为5%时,经MCF抛光10min后材料去除率达到最大值26.4×10~(-4)g/min,表面粗糙度达到最小值8.23nm.MCF中添加适量PVA能够减少抛光液颗粒的团聚,提高MCF的分散性,提升BK7光学玻璃的磁性复合流体抛光性能.     

CSRm二极铁磁场分散性的研究

介绍了国家大科学工程HIRFL-CSR中主环二极磁铁的分散性测量的原理、测量方法，以及垫补的位置和垫补量与磁铁分散大小的关系. 最后给出了CSR主环二极磁铁最终垫补后的分散性结果、测量误差以及影响测量精度的因素.     

Effects of Fractal Size Distributions on Velocity Distributions and Correlations of a Polydisperse Granular Gas

By the Monte Carlo method, the effect of dispersion of disc size distribution on the velocity distributions and correlations of a polydisperse granular gas with fractal size distribution is investigated in the same inelasticity. The dispersion can be described by a fractal dimension D, and the smooth hard discs are engaged in a two- dimensional horizontal rectangular box, colliding inelastically with each other and driven by a homogeneous heat bath. In the steady state, the tails of the velocity distribution functions rise more significantly above a Gaussian as D increases, but the non-Gaussian velocity distribution functions do not demonstrate any apparent universal form for any value of D. The spatial velocity correlations are apparently stronger with the increase of D. The perpendicular correlations are about half the parallel correlations, and the two correlations are a power-law decay function of dimensionless distance and are of a long range. Moreover, the parallel velocity correlations of postcollisional state at contact are more than twice as large as the precollisional correlations, and both of them show almost linear behaviour of the fractal dimension D.     

Imogolite类纳米管直径单分散性密度泛函理论研究

采用密度泛函理论方法研究了三种imogolite类(未取代、NH₂取代和F取代)纳米管的直径单分散性及表面电荷的分布情况, 并从键长方面定性地解释了直径单分散性的原因. 我们给出了IMO, IMO_NH₂和IMO_F的应变能曲线, 结果表明三种纳米管结构的最稳定管径值按照IMO < IMO_NH₂ < IMO_F的顺序递增, 而imogolite类纳米管直径单分散性是由于管径的增大导致内部Si–O, Al–O键与外部Al-OH键键长变化趋势相反造成的, 总之是内部Si–O, Al–O 键和外部Al–OH键相互作用的结果. 此外, 对三种稳定的纳米管结构做了Mulliken布局分析, 并总结了纳米管直径变化对表面电荷的影响. 结果表明正电荷主要积聚在外表面, 而内表面则感应出负电荷, 同时随着纳米管直径的增大表面电荷逐渐增加, 揭示了表面电荷与管径大小的关系. 研究表明, 可以通过改变imogolite内表面不同的官能化取代来控制纳米管直径, 进而调节表面电荷的分布情况, 这在imogolite类材料的分子设计及应用方面有着重要意义.