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.     

Cold sintered,temperature-stable CaSnSiO5-K2MoO4 composite microwave ceramics and its prototype microstrip patch antenna

Dense (1-x)wt%CaSnSiO₅-xwt%K₂MoO₄ (CSSO-KMO) composite ceramics were fabricated by the cold sintering process at 180 °C under 400 MPa for 60 min. X-ray diffraction, Energy dispersive X-ray and Raman spectroscopy confirmed that CSSO and KMO coexisted without intermediate phases. As KMO weight fraction increased, relative permittivity (ε_r) and temperature coefficient of resonant frequency (τ_f) decreased and the microwave quality factor (Q×f, where f is resonant frequency) increased. Near-zero τ_f (-0.5 ppm/°C) was obtained for 65 wt%CSSO-35 wt%KMO with ε_r ～ 9.2 and Q×f ～ 6240 GHz. No chemical reaction between ceramic composites and silver was observed, demonstrating potential for cofiring with Ag-paste. A prototype antenna was fabricated from 65 wt%CSSO-35 wt%KMO composite ceramic with a bandwidth of 144 MHz @ -10 dB, a gain of 5.7 dBi and a total efficiency of 88.4 % at 5.2 GHz, suitable for 5 G mobile communication systems.     

Methods and mechanisms for uniformly refining deformed mixed and coarse grains inside a solution-treated Ni-based superalloy by two-stage heat treatment

The uniform refinement mechanisms and methods of deformed mixed and coarse grains inside a solution-treatment Ni-based superalloy during two-stage annealing treatment have been investigated.The two-stage heat treatment experiments include an aging annealing treatment(AT)and a subsequent recrystallization annealing treatment(RT).The object of AT is to precipitate some δ phases and consume part of storage energy to inhibit the grain growth during RT,while the RT is to refine mixed and coarse grains by recrystallization.It can be found that the recrystallization grains will quickly grow up to a large size when the AT time is too low or the RT temperature is too high,while the deformed coarse grains cannot be eliminated when the AT time is too long or the RT temperature is too low.In addition,the mixed microstructure composed of some abnormal coarse recrystallization grains(ACRGs)and a large number of fine grains can be observed in the annealed specimen when the AT time is 3 h and RT tem-perature is 980℃.The phenomenon attributes to the uneven distribution of δ phase resulted from the heterogeneous deformation energy when the AT time is too short.In the regions with a large number of δ phases,the recrystallization nucleation rate is promoted and the growth of grains is limited,which results in fine grains.However,in the regions with few δ phases,the recrystallization grains around grain boundaries can easily grow up,and the new recrystallization nucleus is difficult to form inside grain,which leads to ACRGs.Thus,in order to obtain uniform and fine annealed microstructure,it is a prereq-uisite to precipitate even-distributed δ phase by choosing a suitable AT time,such as 12 h.Moreover,a relative high RT temperature is also needed to promote the recrystallization nucleation around δ phase.The optimal annealing parameters range for uniformly refining mixed crystal can be summarized as:900℃×12 h+990℃×(40-60 min)and 900℃×12 h+1000℃×(10-15 min).     

Stable Radicals with Protective Umbrellas Integrated on the Surface of 2D Layered Materials

Radicals are closely related to human life and health and have been widely used in biology, chemistry, functional materials, etc. However, the high reactivity, disorder, and short half-lives limit their wide applications. Therefore, it remains a great challenge to prepare stable and ordered radicals. Herein, radicals are prepared with protective umbrellas (diethylmethyleneamine, DEMA) that are integrated on the surface of 2D layered materials to isolate water and oxygen and enhance the stability of radicals. Taking 2D black phosphorus (BP) as an example: triethylamine reacts with dichloromethane to form quaternary ammonium salts with further Hoffmann elimination to produce DEMA radicals that could react with one electron of a lone pair electrons in P on the surface of BP to produce P radicals, which shows a prolonged half-life of 21 days at room temperature. First-principle calculations and electron paramagnetic resonance fitting confirm that the steric hindrance constructed by dense DEMA passivation layer acts as a protective umbrella and the 2D coupling of P radicals and other P atoms in 2D BP plane to enhance the stability and strong superexchange interaction of P radicals. Furthermore, it is a general strategy to produce stable radicals integrated on the 2D plane.     

地铁车辆空气制动管路保压试验的改进方案

分析了地铁车辆空气制动管路组装完毕后的保压试验操作过程,识别了其中的问题项点,提出了有针对性的优化改进方案,使保压试验结果准确可靠.     

Structural insights into peptide self-assembly using photo-induced crosslinking experiments and discontinuous molecular dynamics

Determining the structure of the (oligomeric) intermediates that form during the self-assembly of amyloidogenic peptides is challenging because of their heterogeneous and dynamic nature. Thus, there is need for methodology to analyze the underlying molecular structure of these transient species. In this work, a combination of fluorescence quenching, photo-induced crosslinking (PIC) and molecular dynamics simulation was used to study the assembly of a synthetic amyloid-forming peptide, Aβ_16-22. A PIC amino acid containing a trifluormethyldiazirine (TFMD) group—Fmoc(TFMD)Phe—was incorporated into the sequence (Aβ*_16–22). Electrospray ionization ion-mobility spectrometry mass-spectrometry (ESI-IMS-MS) analysis of the PIC products confirmed that Aβ*_16–22 forms assemblies with the monomers arranged as anti-parallel, in-register β-strands at all time points during the aggregation assay. The assembly process was also monitored separately using fluorescence quenching to profile the fibril assembly reaction. The molecular picture resulting from discontinuous molecule dynamics simulations showed that Aβ_16-22 assembles through a single-step nucleation into a β-sheet fibril in agreement with these experimental observations. This study provides detailed structural insights into the Aβ_16-22 self-assembly processes, paving the way to explore the self-assembly mechanism of larger, more complex peptides, including those whose aggregation is responsible for human disease.     

Flash joining of alumina ceramics under a small current density

The ceramic joining using electric field (E-field) has garnered significant research attention due to the decreased joining barrier and enhanced reliability. However, the underlying mechanism of E-field assisted joining remains unclear. Herein, we report the rapid joining of alumina ceramics using a small current. Moreover, the E-field is applied in both perpendicular and parallel directions to the faying surfaces, demonstrating a significant difference in terms of joint strength. These results indicate that the E-field generates defects and promotes the joining process by facilitating ionic diffusion.     

Negative thermal quenching CsPbBr3 glass-ceramic based on intrinsic radiation and vacancy defect co-induced dual-emission

Halide perovskite glass-ceramic has recently moved into the center of the attention of perovskite research due to their potential for temperature sensing. However, quantum dots glass-ceramic with excellent luminescence performance still needs to be combined with rare-earth (RE) ions to accurately measure temperature. In this work, a novel non-RE doped dual-emission (460 nm and 512 nm) CsPbBr₃ quantum dots was obtained in telluride glass via the friction crystallization method, where 512 nm was derived from intrinsic luminescence of quantum dots, and 460 nm was originated from thermally induced bromine vacancy, which can be used for temperature sensing. Fluorescence intensity ratio results indicate that the relative sensitivity of dual-emission could reach 5.6 % K^?1 at 323 K. The discovery of non-RE doped CsPbBr₃ QDs glass-ceramic with negative thermal quenching uncovers a new optional sensing glass material that surpass traditional RE-doped QDs glass by their tunability and sensitivity.     

无黏土相盐水储层钻开液体系构建及其抗污染性能评价

采用NaCl/KCl/HCOONa复配欠饱和盐水作为钻开液的基础液相,自研的聚合物VIS-B作为流型调节剂,可酸溶的改性淀粉STA作为体系的降失水剂,Dua及Jqw作为暂堵材料,构建了一套无黏土相钻开液体系。该体系在密度1.10~1.28 g/cm^3间稳定可调,抗温可达130℃,具有较高的低剪切速率黏度和较好的润滑性能,且能有效抵抗各类储层污染物的污染,满足了Missan油田不同储层段的作业需求。