Crystallization of Poly(ethylene adipate) within γ-Phase Poly(vinylidene fluoride) Matrix

The effects of PEA on the γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy(OM), infrared spectroscopy(IR) and scanning electron microscopy(SEM). The results demonstrate that the γ-phase PVDF spherulites consist of the lamellae exhibiting a highly curved scroll-like morphology and develop preferentially in PEA-rich blend. With increasing PEA concentration, the scroll diameter increases and the scrolls are better separated from each other. PEA crystallizes first in the interspherulitic region and transcrystalline layer develops. Subsequently, the transcrystalline layer of PEA continues to grow within the γ-phase PVDF spherulites, e.g., in the region between the scrolls, until impinging on other PEA transcrystalline layers or spherulites. The crystallization kinetics results indicate that the growth rate of PEA crystals in the intraspherulitic region of γ-phase PVDF shows a positive correlation with content of PEA, but a negative one with the crystallization temperature of γ-phase PVDF.     

Intermediate Formation of Macrocycles for Efficient Crystallization of 2D Covalent Organic Frameworks with Enhanced Photocatalytic Hydrogen Evolution

Covalent organic frameworks (COFs) have gained significant attention as key photocatalysts for efficient solar light conversion into hydrogen production. Unfortunately, the harsh synthetic conditions and intricate growth process required to obtain highly crystalline COFs greatly hinder their practical application. Herein, we report a simple strategy for the efficient crystallization of 2D COFs based on the intermediate formation of hexagonal macrocycles. Mechanistic investigation suggests that the use of 2,4,6-triformyl resorcinol (TFR) as the asymmetrical aldehyde build block allows the equilibration between irreversible enol-to-keto tautomerization and dynamic imine bonds to produce the hexagonal β-ketoenamine-linked macrocycles, the formation of which could provide COFs with high crystallinity in half hour. We show that COF-935 with 3 wt % Pt as cocatalyst exhibit a high hydrogen evolution rate of 67.55 mmol g⁻¹ h⁻¹ for water splitting when exposed to visible light. More importantly, COF-935 exhibits an average hydrogen evolution rate of 19.80 mmol g⁻¹ h⁻¹ even at a low loading of only 0.1 wt % Pt, which is a significant breakthrough in this field. This strategy would provide valuable insights into the design of highly crystalline COFs as efficient organic semiconductor photocatalysts.     

Three-Dimensional Covalent Organic Frameworks: From Synthesis to Applications

Three-dimensional covalent organic frameworks (3D COFs) with spatially periodic networks demonstrate significant advantages over their 2D counterparts, including enhanced specific surface areas, interconnected channels, and more sufficiently exposed active sites. Nevertheless, research on these materials has met an impasse due to serious problems in crystallization and stability, which must be solved for practical applications. In this Minireview, we first summarize some strategies for preparing functional 3D COFs, including crystallization techniques and functionalization methods. Hereafter, applications of these functional materials are presented, covering adsorption, separation, catalysis, fluorescence, sensing, and batteries. Finally, the future challenges and perspectives for the development of 3D COFs are discussed.     

Mixing of Racemic Poly(L-lactide)/Poly(D-lactide) Blend with Miscible Poly(D,L-lactide):Toward All Stereocomplex-type Polylactide with Strikingly Enhanced SC Crystallizability

Stereocomplex-type polylactide (SC-PLA) consisting of alternatively arranged poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) chains has gained a good reputation as a sustainable engineering plastic with outstanding heat resistance and durability,however its practical applications have been considerably hindered by the weak SC crystallizability.Current methods used to enhance the SC crystallizability are generally achieved at the expense of the precious bio-renewability and/or bio-degradability of PLAs.Herein,we demonstrate a feasible method to address these challenges by incorporating small amounts of poly(D,L-lactide) (PDLLA) into linear high-molecular-weight PLLA/PDLA blends.The results show that the incorporation of the atactic PDLLA leads to a significant enhancement in the SC crystallizability because its good miscibility with the isotactic PLAs makes it possible to greatly improve the chain mixing between PLLA and PDLA as an effective compatibilizer.Meanwhile,the melt stability (i.e.,the stability of PLLA/PDLA chain assemblies upon melting) could also be improved substantially.Very intriguingly,SC crystallites are predominantly formed with increasing content and molecular weight of PDLLA.More notably,exclusive SC crystallization can be obtained in the racemic blends with 20 wt％ PDLLA having weight-average molecular weight of above 1 ×10s g/mol,where the chain mixing level and intermolecular interactions between the PLA enantiomers could be strikingly enhanced.Overall,our work could not only open a promising horizon for the development of all SC-PLA-based engineering plastic with exceptional SC crystallizability but also give a fundamental insight into the crucial role of PDLLA in improving the SC crystallizability of PLLA/PDLA blends.     

Crystallization kinetics and morphology of biodegradable poly(lactic acid) with a hydrazide nucleating agent

The effect of tetramethylenedicarboxylic dibenzoylhydrazide (designated here as TMC) on the nonisothermal and isothermal crystallization behavior of PLA was investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide angle X-ray diffraction (WAXD). TMC shows excellent nucleating effect on PLA. With the addition of 0.05 wt% TMC, the crystallization half-time of PLA decreases from 26.06 to 6.13 min at 130 °C. The isothermal crystallization data were further analyzed by the Avrami model. The values of the Avrami exponent of the blends are comparable to that of neat PLA, indicating that the presence of TMC does not change the crystallization mechanism of the matrix. The observation from POM and WAXD measurements showed that the presence of TMC increases significantly the nuclei density of PLA but has no discernible effect on its crystalline structure.     

Phase structure and crystallization behavior of polyethylene in its blends with cis-1,4-butadiene rubber

Phase structure and crystallization behavior of polyethylene(PE) in its blends with cis-1,4-butadiene rubber(BR) at different blend ratios and sample preparation conditions were studied. The PE is finely dispersed in the BR matrix. For samples hot pressed at 145 °C, circular PE microdomains with randomly oriented PE lamellar aggregates were produced. The domain size and number increase with increasing PE content. When the PE content is over 10 wt%, most of the PE domains impinged each other. The separated PE domains are connected by PE stripes with parallel arranged lamellar aggregates. For samples hot pressed at 140 °C, elongated PE microdomains with oriented PE lamellar aggregates were obtained due to the shear flow. The crystallization of PE in the blends depends on the phase structure. Confined crystallization of PE occurs in small microdomains at relatively low temperature. With the increase of domain size, the crystallization ability of PE increases while the confined crystallization decreases.     

邻位取代基对芳基杂环磷酸盐成核有效性的影响

以2,4-二叔丁基苯酚为原料分别合成2,2'-亚甲基双(4,6-二叔丁基苯基)磷酸钠(NA-1)和2,2'-亚甲基双(4-叔丁基苯基)磷酸钠(NA-2),并将其应用于等规聚丙烯(i PP),研究该类芳基杂环磷酸盐成核剂邻位取代基对其成核有效性的影响.通过红外吸收光谱(FTIR)、核磁共振谱(NMR)、X-Ray多晶粉末衍射(XRD)、扫描电镜分析(SEM)和热分析对其化学结构、凝聚态结构、颗粒形貌和物性特征进行了表征,确定了NA-1和NA-2的分子结构和凝聚态颗粒的结构、形貌和物性特征.利用偏光显微观察(POM)、扫描电镜(SEM)断口分析、示差式扫描量热分析(DSC)和雾度测试分析对其与i PP的复合材料的晶粒结构、结晶行为及宏观光学性能进行测试表征.结果表明,添加量0.2%时,邻位叔丁基(NA-1)的存在可使复合材料球晶尺度更加细密,结晶温度比无邻位叔丁基(NA-2)增加5.1 K,等温结晶速率提高至0.56 w/g是NA-2的7倍,半结晶时间由NA-2的11.55 min下降至2.36 min,邻位叔丁基存在对材料透光率和雾度值的影响分别达到4.3%,7.4%.SEM断口分析表明二者在i PP基体中分散均匀,平均粒径相近分别为0.79μm和0.82μm,粒径分布曲线相近,二者分散分布的差异性不显著.     

Improved Photovoltaic Performance from High Quality Perovskite Thin Film Grown with the Assistance of PC71BM

The strategy of sequentially spin-coating a perovskite film from the perovskite precursor and an electron transporting layer of [6,6]-phenyl-C_(71)-butyric acid methyl ester(PC_(71)BM) is developed to simplify the fabrication procedure of perovskite solar cells. X-ray diffraction and scanning electron microscopy indicate that PC_(71)BM film on perovskite layer can retard the evaporation of dimethyl sulfoxide(DMSO) efficiently, thus prolonging the transformation of intermediate phase to perovskite crystals, leading to a high quality perovskite thin film. The solar cells with the structure of indium tin oxides(ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS)/CH_3NH_3PbI_3/PC_(71)BM/bathocuproine(BCP)/Ag made from this simplified method exhibit a higher efficiency(12.68%) than those from the conventional one-step method(9.49%).     

Isothermal-crystallization kinetics and spherulite growth of aliphatic polyketone/polyamide-6 blends

In this research,the morphologies,isothermal-crystallization kinetics,and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied.A single glass-transition temperature (Tg) was determined,and the composition dependence of Tg for these blends was well described by the Kwei equation.The strong intermolecular interaction between the two polymer components was confirmed by melting-point depression.The isothermal-crystallization kinetics were analyzed on the basis of the Avrami approach.A linear increase in the radii of the spherulites with time was observed for all compositions.All the spherulites continued to grow at nearly identical growth rates.With increasing polyamide-6 content,the size of the spherulites in the polyketone/polyamide-6 blends gradually decreased,and the number of spherulites in the blends increased.     

Co-crystallizing coordination compounds

Crystallization of an equimolar mixture of 1,10-dimethylphenanthroline (DMP) and manganese(II) chloride from N,N-dimethylformamide (DMF) has been studied. Rather than a useful route to a well-defined product, it was found that identical solutions could deposit crystals of three different compounds. The most common outcome was the formation of crystals of [MnCl₂(dmp)(dmf)], 1, or co-crystallization of [MnCl₂(dmp)(dmf)] and [{MnCl₂(dmp)}₂]. The co-crystals, 2, were always found to dissolve as crystals of 1 started to grow. Crystals of a third compound, [MnCl₂(dmp)₂], 3, were also isolated once.