Nucleation‐controlled dual semicrystalline morphology of polyamide 11

Crystallization of polyamide 11 at low supercooling of the melt proceeds via heterogeneous nucleation and spherulitic growth of lamellae, while at temperatures close to the glass transition homogeneous nucleation prevails, preventing spherulite formation and leading to formation of a large number of nanometer‐sized mesophase domains. It is shown that spherulitic and non‐spherulitic crystallization at low and high supercooling of the melt, respectively, can be enforced by tailoring the cooling conditions, causing a twofold semicrystalline morphology at ambient temperature. Analysis of non‐isothermal crystallization as a function of the cooling rate, using fast scanning chip calorimetry, reveals that in the case of polyamide 11 such twofold semicrystalline morphology is predicted when cooling at rates between about 20 and 200 K s^?1, since then two separate crystallization events are observed. The prediction has been confirmed by preparation of films crystallized during ballistic cooling at different rates which then were analyzed regarding their structure using optical microscopy, X‐ray diffraction and calorimetry. The study is completed by discussion of implications of twofold non‐isothermal crystallization for structure evolution in polymer processing, as well as by providing information that such behavior is not only typical for polyamide 11 but also for isotactic polypropylene or poly(butylene terephthalate) as two further examples. © 2018 Society of Chemical Industry     

Form selection of concomitant polymorphs: A case study informed by crystallization kinetics modeling

Molecular mechanisms and process kinetics of crystallizing concomitant polymorphs remain poorly understood. Solvent-mediated phase transformation and concomitant crystallization are difficult to be distinguished in practice, as multiple forms can be detected at the same time. Herein, we developed a population balance model to simulate a concomitant crystallization process of two polymorphs of tolfenamic acid. Our kinetic modeling aims to understand concomitant crystallization and help guide form selection of such a molecular system. Crystallization kinetics of ethanolic solutions were uncovered from induction time measurements, as well as seeded and unseeded crystallization experiments. Experimental and simulation results demonstrate that the stable form I crystallizes concomitantly with the metastable form II. The faster growing form II results in an intermediate decline in the composition of form I in crystallized samples, a characteristic feature of the concomitantly crystallized system. A four-quadrant scheme of attainable polymorph outcome was simulated under various crystallization conditions.     

Effect of different quenching processes following solid-solution treatment on properties and precipitation behaviors of 7050 alloy

The effects of quenching in different ways following solid-solution treatment on properties and precipitation behaviors of 7050 alloy were investigated by transmission electron microscopy (TEM), scanning electron microscopy (SEM), selected area electron diffraction (SAED), hardness and electrical conductivity tests. Results show that after quenching in different ways, electrical conductivity of the alloy decreases rapidly in the first 48 h of natural aging. The electrical conductivity of 7050 alloy in natural aging state is determined by the size and density of GP zones, and the size of GP zones is the main factor. After natural aging for 70 d, the size of GP zones is 1.8–2.6 nm in matrix of the immersion quenched sample and it is 1.4–1.8 nm in matrix of both water mist and forced air quenched samples. After natural and artificial peak aging, the hardness of the water mist quenched sample is HV 193.6 and its electrical conductivity is 30.5% (IACS) which are both higher than those of the immersion quenched sample. Therefore, water mist quenching is an ideal quenching method for 7050 alloy sheets after solid-solution treatment.     

Rapid crystallization of poly(ethylene 2,6-naphthalate) via aryl amide derivatives

ABSTRACT

A very small amount of aryl amide derivative (TMB-5) was used for nucleating Poly(ethylene 2,6-naphathalate) (PEN) by melt blending. The crystalline temperature, crystallinity, and nucleation efficiency of the composites were increased as a result of the addition of TMB-5. The half-time of crystallization decreased upon the addition of TMB-5 and the work required in folding polymer chains were reduced simultaneously in the polymer mixtures. The crystal size of the PEN/TMB-5 blends became smaller due to the increase of nucleation sites. The TMB-5 had no effect on the PEN crystal type. TMB-5 slightly increased the impact strength of PEN.     

平板冲击加载下对双相钢动态损伤演变的研究

利用一级轻汽炮以一击二的方式对2种不同热处理状态的双相钢进行加载,采用多普勒测速系统对加载过程中样品的自由面粒子速度进行测量,通过金相显微分析、纳米压痕分析对样品进行表征,探讨了双相钢的层裂损伤演变。结果表明:孔洞并没有像准静态损伤理论一样在相界面处优先形核长大,而是在马氏体内部形核,然后长大贯通形成微裂纹贯穿整个马氏体,形成穿晶断裂; 由于相界面对冲击波具有反射与透射作用,冲击波从高阻抗的相传入低阻抗的相内时会在高阻抗相内形成拉伸脉冲,从而引起层裂损伤; 相界面越多,在高阻抗相内产生拉应力并形成孔洞的几率越大,样品层裂强度也越低。     

Influence of size-classified and slightly soluble mineral additives on hydration of tricalcium silicate

Early-age hydration of cement is enhanced by slightly soluble mineral additives (ie, fillers, such as quartz and limestone). However, few studies have attempted to systematically compare the effects of different fillers on cementitious hydration rates, and none have quantified such effects using fillers with comparable, size-classified particle size distributions (PSDs). This study examines the influence of size-classified fillers [ie, limestone (CaCO₃), quartz (SiO₂), corundum (Al₂O₃), and rutile (TiO₂)] on early-age hydration kinetics of tricalcium silicate (C₃S) using a combination of experimental methods, while also employing a modified phase boundary and nucleation and growth model. In prior studies, wherein fillers with broad PSDs were used, it has been reported that between quartz and limestone, the latter is a superior filler due to its ability to partake in anion-exchange reactions with C-S-H. Contrary to prior investigations, this study shows that when size-classified and area matched fillers are used—which, essentially, eliminate degrees of freedom associated with surface area and agglomeration of filler particulates—the filler effect of quartz is broadly similar to that of limestone as well as rutile. Results also show that unlike quartz, limestone, and rutile—which enhance C₃S hydration kinetics—corundum suppresses hydration of C₃S during the first several hours after mixing. Such deceleration in C₃S hydration kinetics is attributed to the adsorption of aluminate anions—released from corundum's dissolution—onto anhydrous particulates’ surfaces, which impedes both the dissolution of C₃S and heterogeneous nucleation of C-S-H.     

Validation of Models Predicting Nucleation Rates from Induction Times and Metastable Zone Widths

Three approaches for estimation of nucleation rates from induction time and metastable zone width (MSZW) were validated based on directly measured nucleation rates for paracetamol in ethanol. To quantitatively predict nucleation kinetics using Kubota's methods it is necessary to know the minimum detectable number concentration of nuclei. This was found by determination of light transmission of a series of diluted suspensions of newly nucleated crystals where the size had already been assessed by optical reflection measurement (ORM). The measured nucleation rates strongly depended on both temperature and supersaturation. The Nyvlt method predicted nucleation rates in this system reasonably well; however, it gave slightly low estimates for all temperatures. The methods of Kubota provided nucleation rates that were low by an order of magnitude.     

Controlled Individual Skyrmion Nucleation at Artificial Defects Formed by Ion Irradiation

Magnetic skyrmions are particle‐like deformations in a magnetic texture. They have great potential as information carriers in spintronic devices because of their interesting topological properties and favorable motion under spin currents. A new method of nucleating skyrmions at nanoscale defect sites, created in a controlled manner with focused ion beam irradiation, in polycrystalline magnetic multilayer samples with an interfacial Dzyaloshinskii–Moriya interaction, is reported. This new method has three notable advantages: 1) localization of nucleation; 2) stability over a larger range of external field strengths, including stability at zero field; and 3) existence of skyrmions in material systems where, prior to defect fabrication, skyrmions were not previously obtained by field cycling. Additionally, it is observed that the size of defect nucleated skyrmions is uninfluenced by the defect itself—provided that the artificial defects are controlled to be smaller than the inherent skyrmion size. All of these characteristics are expected to be useful toward the goal of realizing a skyrmion‐based spintronic device. This phenomenon is studied with a range of transmission electron microscopy techniques to probe quantitatively the magnetic behavior at the defects with applied field and correlate this with the structural impact of the defects.     

镁钛复合处理对不锈钢凝固组织的影响及机制

摘要：TiN是铁素体不锈钢有效的异质形核剂，但钢中大尺寸的TiN颗粒会对不锈钢板材表面质量带来不利影响。为此，提出依靠镁钛复合处理来细化TiN颗粒及控制宏观晶粒的方法。通过良好气氛保护的电阻炉试验，研究了添加Mg和Ti元素对于铁素体不锈钢宏观铸态组织和TiN颗粒细化效果的影响规律，并对其细化机理进行了详细分析。经研究得知，向铁素体不锈钢中添加了微量Mg和Ti元素后试样宏观等轴晶比例由37%提高至50%，TiN颗粒平均尺寸由处理前的5μm细化至2μm。镁钛复合处理后，钢液中形成的MgO和MgAl2O4与TiN之间的晶格错配度很低，分别为1.14和5.29，均属于有效形核范围，可以成为TiN异质形核核心，促进在晶内均匀析出更多的TiN。同时基于TiN与铁素体相之间的良好的晶格匹配关系，其进一步促进了δ-Fe形核，从而有效细化了铁素体宏观组织，这将有利于提高铁素体不锈钢力学性能和表面质量。     

Effect of lanthanum-modified magnesium silicate on isotactic polypropylene crystallization in composite materials during shear flow

The activity of isotactic polypropylene (iPP) nucleating additives during shear flow of composite materials is still not entirely explained. In current work the sol-gel method was employed to synthesize MgO·SiO₂ filler, surface-modified with trivalent lanthanum. The crystallization of commercial iPP in the presence of 0.5% by weight La³⁺ modified or unmodified silicates was analyzed. The wide angle X-ray scattering analysis proved that the presence of even small amount of filler influences significantly on supermolecular structure of iPP. The results of microscope observations confirmed that the lanthanum-modified filler shows the nucleating ability for iPP. In that case a significant reduction of crystallization induction time was noticed. The investigation of iPP crystallization in composites after shear treatment confirmed that the increase of shear rate reduces the nucleating ability of additives. Moreover, the flow of filler particles during shearing may impede the shear-induced crystallization phenomenon.