A DSC study of the effects of sugars on thermal properties of rice starch gels before and after aging

Thermal characterization of gelatinized binary rice starch-water and ternary starch-sugar-water gels before and after aging was carried out using differential scanning calorimetry. The glass transition temperature of the maximally freeze-concentrated solution (T_g) in both fresh and aged gels was observed to decrease progressively with increasing sugar concentration. Aging of the gels generally shiftedT_g to higher temperatures, but had little or no effect on the ice melting peak temperature (T _m). The presence of various sugars could either accelerate or retard starch (amylopectin) recrystallization, depending on the type and concentration of sugar, as well as on starch/water ratio. A hypothesis based on the dual antiplasticizing-plasticizing effects of sugars was postulated to explain the observed effects. Of the sugars studied, xylose and fructose appeared to display exceptional retardative and accelerative effects, respectively, on retrogradation.This study was funded by a Sixth Malaysia Plan R&D grant under the Intensification of Research Priority Areas (IRPA) Program of the Ministry of Science, Technology and Environment, Malaysia. We thank Dr. Harry Levine and Dr. Louise Slade for giving us the opportunity to contribute a paper to this special issue of JTA.     

氟化钾团簇的相变、成核和重结晶的分子动力学模拟

我们利用Born-Mayer-Huggins相互作用势函数对(KF)_N(N=108，256，500和864)团簇进行了分子动力学(MD)模拟。为了避免周期性边界条件对相变、成核和重结晶的干扰作用，对体系采用了自由边界。基于MD模拟结果，对团簇的熔化温度、熔化焓、扩散系数、成核速率、固液界面自由能、临界核大小等进行了计算和讨论。在对(KF)₈₆₄双晶团簇的热退火模拟中，观察到了固态的重结晶和晶粒的生长。经典的成核理论成功地解释了(KF)₈₆₄双晶团簇的重结晶MD模拟结果。     

Cyanex301的纯化及其特性

研究了用Ｃｙａｎｅｘ３０１［ＴＭ］铵盐在苯中重结晶以纯化Ｃｙａｎｅｘ３０１的方法，该法收率６２．４％，产品纯度＞９９％。测定了经纯化后产品的红外光谱，研究了纯化产品在－水正庚烷体系中的分配平衡及其在正庚烷中的缔合，浓度在０．２～１．０ｍｏ１／Ｌ范围，Ｃｙａｎｅｘ３０１主要以二聚形式存在。     

Synthesis and crystallization behavior of rigid copolyesters with biphenyl‐4,4′‐dicarboxylate and 2,6‐naphthalenedicarboxylate in the main chain

Structurally rigid copolyester thermoplastics were synthesized from 1,4‐cyclohexanedimethanol and the diesters dimethyl biphenyl‐4,4′‐dicarboxylate and dimethyl 2,6‐naphthalenedicarboxylate (DMN) via conventional melt transesterification. Conventional differential scanning calorimetry (CDSC) showed all compositions to exhibit multiple endotherms upon heating. Wide‐angle X‐ray diffraction analysis showed copolyester compositions to exhibit the crystalline structure of either the homopolyester Poly(1,4‐cyclohexylenedimethylene 2,6‐naphthalate) (PCN) or the homopolyester Poly(1,4‐cyclohexylenedimethylene 4,4′‐bibenzoate) (PCB), but not both simultaneously. Further thermal analysis using CDSC and fast DSC investigated the origin of the multiple endotherm behavior. While three endotherms are observed for low heating rates, the upper two endotherms appear to merge at heating rates about 1–5 °C s^?1 and a single endotherm remains above heating rates about 10–50 °C s^?1. While the behavior of the upper two endotherms is undeniably consistent with the mechanism of melting–recrystallization–remelting (MRR), we suggest that the low endotherm is likely associated with the melting of constrained secondary crystals, although MRR effects cannot be ruled out. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 973–980     

Nonclassical Recrystallization

Applications in the fields of materials science and nanotechnology increasingly demand monodisperse nanoparticles in size and shape. Up to now, no general purification procedure exists to thoroughly narrow the size and shape distributions of nanoparticles. Here, we show by analytical ultracentrifugation (AUC) as an absolute and quantitative high-resolution method that multiple recrystallizations of nanocrystals to mesocrystals is a very efficient tool to generate nanocrystals with an excellent and so-far unsurpassed size-distribution (PDI_c=1.0001) and shape. Similar to the crystallization of molecular building blocks, nonclassical recrystallization removes “colloidal” impurities (i.e., nanoparticles, which are different in shape and size from the majority) by assembling them into a mesocrystal. In the case of nanocrystals, this assembly can be size- and shape-selective, since mesocrystals show both long-range packing ordering and preferable crystallographic orientation of nanocrystals. Besides the generation of highly monodisperse nanoparticles, these findings provide highly relevant insights into the crystallization of mesocrystals.     

Initial lamellar thickness dependency of recrystallization behavior of poly(4‐methyl‐1‐pentene)

The isothermal crystallization and subsequent melting process in semicrystalline poly(4‐methyl‐1‐pentene) were investigated via temperature‐dependent small‐ and wide‐angle X‐ray scattering and Flash DSC techniques. In a phase diagram of inversed crystalline lamellar thickness and temperature, the crystallization and melting lines can be described by two linear dependencies of different slopes and different limiting temperatures at infinite lamellar thickness. Upon subsequent heating, recrystallization lines with different slopes were observed for samples with different lamellar thickness, indicating changes in surface free energy difference between stabilized crystallites and mesomorphic phase. The surface free energy of native crystallites with extended‐chain conformation decreased with increasing lamellar thickness due to a more ordered surface region and less chain ends which changes cooperatively with mesomorphic phase. The surface free energy of stabilized crystallites remained unchanged for all lamellar thickness. Therefore, the recrystallization lines with different slopes are consequences of changes in surface free energy of mesomorphic phase. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 219–224     

Controllable synthesis of high aspect ratio Mg_2B_2O_5 nanowires and their applications in reinforced polyhydroxyalkanoate composites

Highly pure magnesium borate （Mg2B2O5） nanowires with an average diameter of - 30 nm, an average length of 15 μm, and a high aspect ratio of - 500 have been synthesized on a large scale via a two-step method. MgBO2（OH） nanowires with high aspect ratios were first prepared via a PVP-assisted hydrothermal technique. Using these nanowires as precursors, single crystalline Mg2B205 nanowires were synthesized by post-annealing treatment at a relatively low temperature of 700 ℃. The important effect of the MgBO2（OH）-Mg2B2O5 conversion process on the morphology of the Mg2B2O5 nanowires was investigated and it was indicated that the recrystallization process plays an important role in the protection of the one-dimensional （1D） nanostructure. Moreover, the rigidity and the toughness of the Mg2B2O5 nanowire- reinforced PHA composites were tremendously improved compared to those of the pure PHA. Our results demonstrate the effectiveness of Mg2B2O5 nanowires for reinforcement applications in polymer composites.     

两相钛合金再结晶退火组织与织构演变的蒙特卡罗模拟

蒙特卡罗(MC)方法被广泛应用于模拟金属材料在退火过程中的静态再结晶行为. 在已有两相材料晶粒长大MC模型基础上, 引入形核阶段, 综合考虑再结晶晶粒吞并形变晶粒和再结晶晶粒竞争长大两种情况, 建立了退火时两相合金再结晶MC模型.结合电子背散射衍射所测 初始晶粒形貌、相成分、晶体学取向及应变储能相对值, 该模型被应用于TC11钛合金退火过程中的微观组织及织构演变模拟.结果表明, 所建模型能够较好体现退火过程中两相晶粒的形核及晶粒长大行为. 与β相相比较, α相具有较低的再结晶速率和较高的晶粒长大速率, 前者主要归结于α相较低的初始应变储能, 后者则体现了该条件下初始组织形貌、分布及两相比例对晶粒长大具有重要影响; 由于非均匀形核的影响, 模拟得到的再结晶速率变化与 假设均匀形核的Johnson-Mehl-Avrami-Kolmogorov 再结晶方程存在明显差异.同时, 两相的基本织构特征在退火过程中无明显变化, 但织构强度增加. 关键词： 两相钛合金 再结晶 蒙特卡罗方法 织构     

动态载荷下剪切变形局部化、微结构演化与剪切断裂研究进展

总结和评述了近年来金属与合金变形局部化的形成、微结构演化与剪切断裂方面作者和相关的研究工作成果. 材料包括低碳钢, SS304不锈钢, Fe-15%Ni-15%Cr单晶, Al-Li合金,α-Ti和Ti-6Al-4V, Al/SiCp复合材料等.综述内容主要包括:采用改进的Hopkinson扭杆装置,对剪切变形局部化形成、发展和演化过程进行了实验观察与数值模拟;采用"侧剖"与"对接"等定点方法制备电子显微镜薄膜试样,对剪切带内相变与再结晶、非晶转变、旋涡结构等动态变形现象,以及与宏观动态力学行为对应的位错胞的形成、发展和坍塌等微结构特征进行了观测;提出了应变和应变率同时作为剪切带形成的两个必要条件的直接实验证据;在剪切带内发现了α'$-马氏体相变现象,以及相变产物与母体之间的晶体学关系;通过位错单滑移或交滑移等微观剪切最后发展成为宏观剪切的机制;对剪切带内再结晶结构的观测和对再结晶动力学本构关系的定量描述;对剪切带特别是``白色'腐蚀带(或相变带)的形成机制的分析和新的解释,指出 ``白色'是带内亚结构取向趋于一致,其在光学或扫描显微镜下很难辨认这些亚结构的取向差所致,并非表明剪切带内一定发生了相变;通过截断实验和实时跟踪观测发现,剪切带内微裂纹的萌生与聚合是材料承载能力骤然下降并导致最后断裂的主控因素.此外,本文对近年来在准静态和循环加载下材料的局部化形变与剪切断裂的实验结果予以简要评述,指出其微观机制与动态载荷下的截然不同, 是由位错的平面滑移所控制的,与热效应无关的等温变形.      

银杏叶提取物中染料木素的分离纯化及结构鉴定

对银杏叶提取物进行酸水解,然后利用正相硅胶柱色谱及重结晶法从银杏叶水解物中分离出染料木素,经紫外光谱（UV）、质谱（MSn）、核磁共振（1H NMR、13C NMR）等波谱学方法鉴定证实了其结构。高效液相色谱分析表明,所提纯的染料木素纯度达到了98%以上。