水铝英石/PEO/LiClO4复合固态聚合物电解质中组分相互作用对PEO结晶的影响

为解决现有锂离子电池的安全性问题,固态电解质的研究备受关注。以Na2SiO3和AlCl3·6H2O为原料,采用溶胶-凝胶法制备出水铝英石(AL);通过溶液共混法将其与聚环氧乙烷/高氯酸锂(PEO/LiClO4)复合得到复合固态聚合物电解质。利用X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、差示扫描量热分析仪(DSC)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)以及光学显微镜(OM)对样品进行结构分析及形貌表征。结果表明:水铝英石和LiClO4与PEO间的非价键力相互作用(络合、氢键及Lewis酸-碱作用)显著抑制PEO的结晶。随着水铝英石含量的增加,PEO的结晶度呈现出先降低后增加的趋势;而随着锂盐含量的增加,PEO的结晶度持续降低,当EO/Li+摩尔比为10∶1,水铝英石的含量为5%(质量分数)时,复合固态聚合物电解质的结晶度最低,仅为4.12%。     

Programmable Atom Equivalents: Atomic Crystallization as a Framework for Synthesizing Nanoparticle Superlattices

Decades of research efforts into atomic crystallization phenomenon have led to a comprehensive understanding of the pathways through which atoms form different crystal structures. With the onset of nanotechnology, methods that use colloidal nanoparticles (NPs) as nanoscale “artificial atoms” to generate hierarchically ordered materials are being developed as an alternative strategy for materials synthesis. However, the assembly mechanisms of NP‐based crystals are not always as well‐understood as their atomic counterparts. The creation of a tunable nanoscale synthon whose assembly can be explained using the context of extensively examined atomic crystallization will therefore provide significant advancement in nanomaterials synthesis. DNA‐grafted NPs have emerged as a strong candidate for such a “programmable atom equivalent” (PAE), because the predictable nature of DNA base‐pairing allows for complex yet easily controlled assembly. This Review highlights the characteristics of these PAEs that enable controlled assembly behaviors analogous to atomic phenomena, which allows for rational material design well beyond what can be achieved with other crystallization techniques.     

分散相含量对乙烯-醋酸乙烯酯共聚物/聚丙烯原位微纤复合材料微纤形态、结晶行为及流变和力学性能的影响

利用微纳层叠共挤出装置成功制得EVA/PP原位微纤复合材料(MFCs),并对其微纤形态、力学性能、结晶性能和流变行为进行了研究。结果表明:PP在EVA中能够形成微纤,且随PP含量增加,直径较大的微纤数量显著增多,MFCs的储能模量(G′)和损耗模量(G″)都相应增大。且当PP含量低于10%(质量分数,下同)时,复合材料体系是部分相容的,但当PP含量超过10%时,体系发生相分离现象。PP微纤能够有效提高EVA的拉伸强度。当PP含量为20%时,拉伸强度最大,为16.71MPa,比纯EVA树脂提高了42.9%。差示扫描量热法(DSC)测试显示PP微纤会阻碍EVA的结晶行为,使MFCs的结晶度降低。     

MgO/Al2O3比对MgO-Al2O3-SiO2系统玻璃分相与析晶的影响

采用高温熔融法制备了具有不同MgO/Al₂O₃比的堇青石微晶玻璃。采用差热分析仪(DTA)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)等测试技术研究了MgO/Al₂O₃比对该系统玻璃分相和析晶的影响。结果表明:当SiO₂含量不变时,随着MgO/Al₂O₃比的减小,分相形貌由连通的蠕虫状逐渐变为孤立的球形结构,且分相粒子尺寸逐渐减小,从200~300 nm减小至30~50 nm。当MgO/Al₂O₃比从3降到1,析晶峰温度由997 ℃升至1 105 ℃,析晶的难度逐渐提高。当MgO/Al₂O₃比为3时,MgO-Al₂O₃-SiO₂系统玻璃经950 ℃热处理后即产生大量分相,经1 050 ℃热处理后在分相液滴中析出大量堇青石晶体,且堇青石优先在富Mg相中析出。提高MgO/Al₂O₃比有利于MgO-Al₂O₃-SiO₂系统玻璃在分相中析晶,反之,则会降低系统的分相和析晶能力。     

In Situ Growth of 120 cm2 CH3NH3PbBr3 Perovskite Crystal Film on FTO Glass for Narrowband‐Photodetectors

Organometal trihalide perovskites have been attracting intense attention due to their enthralling optoelectric characteristics. Thus far, most applications focus on polycrystalline perovskite, which however, is overshadowed by single crystal perovskite with superior properties such as low trap density, high mobility, and long carrier diffusion length. In spite of the inherent advantages and significant optoelectronic applications in solar cells and photodetectors, the fabrication of large‐area laminar perovskite single crystals is challenging. In this report, an ingenious space‐limited inverse temperature crystallization method is first demonstrated to the in situ synthesis of 120 cm² large‐area CH₃NH₃PbBr₃ crystal film on fluorine‐doped tin oxide (FTO) glass. Such CH₃NH₃PbBr₃ perovskite crystal film is successfully applied to narrowband photodetectors, which enables a broad linear response range of 10^?4–10² mW cm^?2, 3 dB cutoff frequency (f _{3 dB}) of ≈110 kHz, and high narrow response under low bias ?1 V.     

聚丙烯接枝马来酸酐改性纳米ZnO/聚丙烯复合材料的成核结晶行为及力学性能

采用熔融共混法制备了nano-ZnO/聚丙烯(PP)复合材料,研究了相容剂聚丙烯接枝马来酸酐(PP-gMAH)的加入对nano-ZnO/PP复合材料的成核结晶行为、晶体结构、结晶形态以及力学性能的影响。结果表明,低添加量(质量分数小于5%)的nano-ZnO对PP有较好的β晶成核效应,而当其质量分数大于5%时,nano-ZnO对PP结晶有明显的异相成核作用,使PP结晶温度大幅度提高,PP结晶在(040)晶面呈现生长择优性;PP-gMAH的加入增强了nano-ZnO粒子与PP基体之间的界面相互作用,改善了纳米粒子的分散性,促进了PP基体的异相成核,提高了nano-ZnO/PP复合材料的拉伸强度和冲击强度,但却抑制了nano-ZnO诱导PP生成β晶。nano-ZnO/PP复合材料体系中因界面相互作用改善所致的韧性提高明显强于nano-ZnO诱导PP形成β晶的增韧效应。     

Pharmaceutical formulation and manufacturing using particle/powder technology for personalized medicines

Particle/powder technology is used in the manufacture of many pharmaceutical products, and research on the physical properties of particles in the nano- to micro-particle range is important in the pharmaceutical field. The concept of precision medicine will require an increasing shift in pharmaceutical manufacturing toward the design of individualized products. This perspective article focuses on particle design and powder technology for advanced formulations that will be needed in the future for individualized drug formulations and on-demand production. Nanoparticles as drug carriers in drug delivery systems will require particle designs to meet the treatment requirements of individual patients with a particular disease. In pharmaceutical manufacturing, process intensification, such as continuous manufacturing and integrated drug production from drug synthesis to final formulation, has attracted increased attention. Digital design approaches, such as artificial intelligence based on computer-aided development, also will be increasingly used. Continuous production of pharmaceutical products enables downsizing of manufacturing equipment, and on-demand manufacturing equipment has been developed. In addition, additive manufacturing, such as 3D printing, is considered to be suitable for personalized formulations, and small-scale powder handling and predictive modeling of powder characterization will be important for individual preparations.     

Unraveling the Crystallization Kinetics of 2D Perovskites with Sandwich-Type Structure for High-Performance Photovoltaics

2D perovskite solar cells with high stability and high efficiency have attracted significant attention. A systematical static and dynamic structure investigation is carried out to show the details of 2D morphology evolution. A dual additive approach is used, where the synergy between an alkali metal cation and a polar solvent leads to high-quality 2D perovskite films with sandwich-type structures and vertical phase segregation. Such novel structure can induce high-quality 2D slab growth and reduce internal and surface defects, resulting in a high device efficiency of 16.48% with enhanced continuous illumination stability and improved moisture (55–60%) and thermal (85 °C) tolerances. Transient absorption spectra reveal the carrier migration from low n to high n species with different kinetics. An [PbI₆]⁴⁻ octagon coalescence transformation mechanism coupled with metal and organic cations wrapped is proposed. By solvent vapor annealing, a recrystallization and reorientation of the 2D perovskite slabs occurs to form an ideal structure with improved device performance and stability.     

Bioinspired Stable and Photoluminescent Assemblies for Power Generation

Peptide assemblies are ideal components for eco‐friendly optoelectronic energy harvesting devices due to their intrinsic biocompatibility, ease of fabrication, and flexible functionalization. However, to date, their practical applications have been limited due to the difficulty in obtaining stable, high‐performance devices. Here, it is shown that the tryptophan‐based simplest peptide cyclo‐glycine‐tryptophan (cyclo‐GW) forms mechanically robust (elastic modulus up to 24.0 GPa) and thermally stable up to 370 °C monoclinic crystals, due to a supramolecular packing combining dense parallel β‐sheet hydrogen bonding and herringbone edge‐to‐face aromatic interactions. The directional and extensive driving forces further confer unique optical properties, including aggregation‐induced blue emission and unusual stable photoluminescence. Moreover, the crystals produce a high and sustained open‐circuit voltage (1.2 V) due to a high piezoelectric coefficient of 14.1 pC N^?1. These findings demonstrate the feasibility of utilizing self‐assembling peptides for fabrication of biointegrated microdevices that combine high structural stability, tailored optoelectronics, and significant energy harvesting properties.     

Multi-Level Information Encryption/Decryption of Fluorescent Hydrogels Based on Spatially Programmed Crystal Phases

The growing urgence of information protection promotes continuously the development of information-encryption technique. To date, hydrogels have become an emerging candidate for advanced information-encryption materials, because of their unique stimulus responsiveness. However, current methods to design multi-level information-encrypted hydrogels usually need sophisticated chemistry or experimental setup. Herein, a novel strategy is reported to fabricate hydrogels with multi-level information encryption/decryption functions through spatially programming the polymorphic crystal phases. As homocrystalline and stereocomplex crystal phases in fluorescent hydrogels have different solvent stabilities, the transparency and fluorescence of the hydrogels can be regulated, thereby enabling the multi-level encryption/decryption processes. Moreover, the structural origins behind these processes are discussed. It is believe that this work will inspire future research on developing advanced information-encryption materials upon programming the polymer crystal structure.