Free energy of conformational change in a single chain of polyvinylidene fluoride using molecular simulations

Polyvinylidene fluoride (PVDF) has several crystal forms of which the α-form is nonpolar, while the β-form is polar and has the highest piezoelectric constant. α PVDF, when stretched, transforms into the β form, which has wide applications in sensors and actuators. Steered molecular dynamics simulations are used to study the transformation of a single chain of PVDF from a trans–gauche conformation to an all trans one. The Helmholtz free energy change (∆F) is estimated using Jarzynski's equality. The transformation starts at the chain ends followed by the transformation of the remaining chain. The free energy change for the transformation is found to be always positive, indicating that the TGTG' form has higher thermodynamic stability than the all trans form throughout the studied temperature range. With increasing temperature, free energy change for the transformation increases monotonically.     

Tuning of shear thickening behavior and elastic strength of polyvinylidene fluoride via doping of ZnO-graphene

ZnO rice like nonarchitects are grafted on the graphene carbon core via a rapid microwave synthesis route. The prepared grafted systems are characterized via XRD, SEM, RAMAN, and XPS to examined the structural and morphological parameters. Zinc oxide grafted graphene sheets (ZnO-G) are further doped in β-phase of polyvinylidene fluoride (PVDF) to prepare the polymer nanocomposites (PNCs) via mixed solvent approach (THF/DMF). β-phase confirmation of PVDF PNCs is done by FTIR studies. It is observed that ZnO-G filler enhances the β-phase content in the PNCs. Non-doped PVDF and PNCs are further studied for rheological behavior under the shear rate of 1–100 s⁻¹. Doping of ZnO-G dopant to the PVDF matrix changes its discontinuous shear thickening (DST) behavior to continues shear thickening behavior (CST). Hydrocluster formation and their interaction with the dopant could be the reason for this striking DST to CST behavioral change. Strain amplitude sweep (10⁻³% -10%) oscillatory test reveals that the PNCs shows extended linear viscoelastic region with high elastic modulus and lower viscous modulus. Effective shear thickening behavior and strong elastic strength of these PNCs present their candidature for various fields including mechanical and soft body armor applications.     

Maskless Preparation of Spatially-Resolved Plasmonic Nanoparticles on Polydimethylsiloxane via In Situ Fluoride-Assisted Synthesis

Here, a fluoride-assisted route for the controlled in-situ synthesis of metal nanoparticles (NPs) (i.e., AgNPs, AuNPs) on polydimethylsiloxane (PDMS) is reported. The size and coverage of the NPs on the PDMS surface are modulated with time and over space during the synthetic process, leveraging the improved yield (10×) and faster kinetics (100×) of NP formation in the presence of F⁻ ions, compared to fluoride-free approaches. This enables the maskless preparation of both linear and step gradients and patterns of NPs in 1D and 2D on the PDMS surface. As an application in flexible plasmonics/photonics, continuous and step-wise spatial modulations of the plasmonic features of PDMS slabs with 1D and 2D AgNP gradients on the surface are demonstrated. An excellent spatially resolved tuning of key optical parameters, namely, optical density from zero to 5 and extinction ratio up to 100 dB, is achieved with AgNP gradients prepared in AgF solution for 12 minutes; the performance are comparable to those of commercial dielectric/interference filters. When used as a rejection filter in optical fluorescence microscopy, the AgNP-PDMS slabs are able to reject the excitation laser at 405 nm and retain the green fluorescence of microbeads (100 µm) used as test cases.     

Effects of corrosion in liquid fluoride salt on the tensile strength of domestic SiC fibers

The relationship between the tensile strength of corroded domestic second-generation (2ed-gen) SiC fibers at various temperatures for 500 h in 46.5LiF-11.5NaF-42.0KF (mol. %) eutectic salt and the typical microstructure was studied. Weibull theory was used to analyze the critical defects that caused the tensile fracture, and the microstructure of fibers before and after corrosion was characterized. It is concluded that the decrease of tensile strength after corrosion at 800 °C is caused by the surface injury of fibers, which led to the shift of critical defects from the internal defects of virgin fibers to surface defects. Moreover, corrosion at higher temperature accelerates the corrosion process and dissolve the surface O-contained layer thoroughly. This shifts the critical defects back to the internal defects and will be helpful for the recovery of tensile strength of corroded fibers at the higher temperature.     

Enhanced dielectric and piezoelectric properties in potassium sodium niobate/polyvinylidene fluoride composites using nano-silicon carbide as an additive

Piezoelectric materials are an indispensable part of modern life. Yet the existing environmental issues with conventional lead-based piezoelectrics has motivated scientist to develop novel substitutes including lead-free piezoelectric polymer composites. Following this path, the present research has focused on the fabrication of ternary composites of Polyvinylidene fluoride (PVDF)/Potassium Sodium Niobate (KNN)/nano-Silicon carbide (SiC) via hot compression molding and studying the effect of additives on the PVDF structure and the electrical properties of the composite. The obtained scanning electron micrographs and density measurements showed that the fabrication method provided dense samples. The activated polarization phenomena in the prepared samples enhanced dielectric permittivity and dielectric loss at a constant frequency with increasing KNN and SiC contents. Besides the expected dipole polarization, the presence of interfaces in the composites gave rise to the Maxwell–Wagner–Sillars effect and its corresponding polarization phenomenon. The semiconductive nature of SiC also promoted space charge polarization. However, these properties were frequency-dependent because the first two polarization mechanisms are deactivated at high frequencies. XRD patterns showed that SiC addition can alter the primary crystalline structure of PVDF and promote β-phase formation in the poled samples. Piezoelectric measurements confirmed the significant role of SiC addition to PVDF-KNN composites. The most significant increase in the piezoelectric properties was observed in PVDF-60KNN-1SiC, with a 183% increase in d₃₃ value. The PVDF-80KNN-1SiC had the highest d₃₃ value of 30.5 pC/N. It also had the best piezoelectric voltage coefficient and hence the highest figure of merit. Higher SiC contents restrict the efficiency of poling by forming a conductive path across the sample which would deteriorate the piezoelectric performance of the material. The present findings show that PVDF-KNN-SiC composites can be considered as a potential flexible piezoelectric material for future applications.     

硫酸体系中锰钽铌矿加压浸出研究

针对单一硫酸体系锰钽铌矿加压浸出下钽铌浸出率均不到10%的问题,在硫酸体系引入助浸剂,考察氟化铵、双氧水、反应压强、硫酸浓度、反应温度、氟化铵矿比对锰钽铌矿加压浸出的影响,采用XRD对浸渣进行物相表征。实验结果表明,在锰钽铌矿加压浸出中,引入助浸剂氟化铵,温度200℃、硫酸浓度50%及氟化铵/矿比为0.8∶1的条件下钽浸出率超过93%,铌浸出率超过96%。引入氟化铵对硫酸体系下锰钽铌矿的加压浸出效果的提升十分显著。     

A Dynamic Memory Allocation Optimization Mechanism Based on Spark

Spark is a distributed data processing framework based on memory. Memory allocation is a focus question of Spark research. A good memory allocation scheme can effectively improve the efficiency of task execution and memory resource utilization of the Spark. Aiming at the memory allocation problem in the Spark2.x version, this paper optimizes the memory allocation strategy by analyzing the Spark memory model, the existing cache replacement algorithms and the memory allocation methods, which is on the basis of minimizing the storage area and allocating the execution area according to the demand. It mainly including two parts: cache replacement optimization and memory allocation optimization. Firstly, in the storage area, the cache replacement algorithm is optimized according to the characteristics of RDD Partition, which is combined with PCA dimension. In this section, the four features of RDD Partition are selected. When the RDD cache is replaced, only two most important features are selected by PCA dimension reduction method each time, thereby ensuring the generalization of the cache replacement strategy. Secondly, the memory allocation strategy of the execution area is optimized according to the memory requirement of Task and the memory space of storage area. In this paper, a series of experiments in Spark on Yarn mode are carried out to verify the effectiveness of the optimization algorithm and improve the cluster performance.     

城市污水厂剩余污泥对水中F-的吸附性能研究

利用城市污水处理厂的剩余污泥对水中F-进行吸附处理,通过污泥投加量、F-初始质量浓度、时间、pH等反应条件的研究,探讨除氟效果和影响因素。结果表明,室温下,污泥对F-的吸附在60 min后达到平衡;20 g/L的污泥投加量对10 mg/L含氟水的F-去除率可达83.1%;污泥可在3~10的较大pH范围内保持稳定的除氟效果。准二级动力学模型很好地拟合了污泥对F-的吸附行为,Langmuir和Freundlich模型均符合污泥对F-的吸附特性,热力学参数的计算表明该吸附过程是自发的放热反应。