Assessment of conservative weighting scheme in simulating chemical vapour deposition with trace species

Low‐pressure or ultra‐high vacuum chemical vapour deposition often involves important trace species in both gas‐phase and surface reactions. The conservative weighting scheme (J. Thermophys. Heat Transfer 1996; 10 (4) : 579) has been used to deal with the trace species often involved in some non‐reactive physical processes, which is otherwise considered computationally impossible using the conventional DSMC method. This conservative weighting scheme (CWS) improves greatly the statistical uncertainties by decreasing the weighting factors of trace‐species particles and ensures the conservation of both momentum and energy between two colliding particles with large difference of weighting factors. This CWS is further extended to treat reactive processes for gas‐phase and surface reactions with trace species, which is called extended conservative weighting scheme (ECWS). A single‐cell equilibrium simulation is performed for verifying both the CWS and ECWS in treating trace species. The results of using CWS show that it is most efficient and accurate for weight ratio (trace to non‐trace) equal to or less than 0.01 for flows with two and three species. The results of a single‐cell simulation using ECWS for gas‐phase reaction and surface reactions show that only ECWS can produce acceptable results with reasonable computational time. Copyright © 2003 John Wiley & Sons, Ltd.     

Creep crack growth on spent fuel zircaloy cladding in interim storage

The effect of creep failure mechanisms on the creep crack growth is examined on spent fuel Zircaloy cladding in interim storage. Based on the creep fracture mechanics parameter C^* and the strain energy density criteria, the relationship between the creep crack growth rate and the fracture mechanics parameter C^* is established theoretically. The effects of initial crack lengths and storage temperature profiles on cladding failure are discussed in detail. The results show that the initial crack length and the storage temperature profile play an important role in the interim dry storage. When the storage temperature remains at a constant temperature of 400 °C, it will be safe for the cladding which stores in the interim dry storage. The results presented in this study provide a reliable cladding integrity evaluation for spent fuel in the interim dry storage.     

High-speed monitoring of the crystallinity change in poly(lactic acid) during photodegradation by using a newly developed wide area NIR imaging system (Compovision)

We aimed to achieve wide area rapid monitoring of the crystallinity change in poly(lactic acid) (PLA) during photodegradation caused by ultraviolet (UV) light by using a newly developed near-infrared (NIR) camera (Compovison). Several kinds of PLA samples with different crystallinities and their blends with poly[(3)-(R)-hydroxybutyrate] were prepared. Their two-dimensional NIR spectra in the 1,000–2,350-nm region were measured by Compovision at a 5-min interval during photolysis. An intensity decrease of the band in the 1,900-1,925-nm region due to the second overtone of the C = O stretching vibration of PLA was observed during photolysis. This suggests that an anhydride carbonyl is produced during photolysis. The NIR image of the crystallinity change monitored by the band at 1,917 nm in the standard normal variate spectra clearly shows the inhomogeneity of crystal evolution. A logarithmic increase was observed for all identified areas in the PLA film; however, the time to reach the maximum crystallinity was slightly different according to the initial crystallinity of the sample. It is likely that the initial crystallinity of the sample influences the degradation speed more than the degradation amount. These imaging results have provided fundamental chemical insights into the photolytic process for PLA, and at the same time they have demonstrated that the two-dimensional spectral data obtained by Compovision are useful for process monitoring of polymers.     

Active dielectric metasurface based on phase‐change medium

We propose all‐dielectric metasurfaces that can be actively re‐configured using the phase‐change material Ge₂Sb₂Te₅ (GST) alloy. With selectively controlled phase transitions on the composing GST elements, metasurfaces can be tailored to exhibit varied functionalities. Using phase‐change GST rod as the basic building block, we have modelled metamolecules with tunable optical response when phase change occurs on select constituent GST rods. Tunable gradient metasurfaces can be realized with variable supercell period consisting of different patterns of the GST rods in their amorphous and crystalline states. Simulation results indicate a range of functions can be delivered, including multilevel signal modulating, near‐field coupling of GST rods, and anomalous reflection angle controlling. This work opens up a new space in exploring active meta‐devices with broader applications that cannot be achieved in their passive counterparts with permanent properties once fabricated.

     

Recent trends in nanomaterial-based microanalytical systems for the speciation of trace elements: A critical review

Trace element speciation in biomedical and environmental science has gained increasing attention over the past decade as researchers have begun to realize its importance in toxicological studies. Several nanomaterials, including titanium dioxide nanoparticles (nano-TiO₂), carbon nanotubes (CNTs), and magnetic nanoparticles (MNPs), have been used as sorbents to separate and preconcentrate trace element species prior to detection through mass spectrometry or optical spectroscopy. Recently, these nanomaterial-based speciation techniques have been integrated with microfluidics to minimize sample and reagent consumption and simplify analyses. This review provides a critical look into the present state and recent applications of nanomaterial-based microanalytical systems in the speciation of trace elements. The adsorption and preconcentration efficiencies, sample volume requirements, and detection limits of these nanomaterial-based speciation techniques are detailed, and their applications in environmental and biological analyses are discussed. Current perspectives and future trends into the increasing use of nanomaterial-based microfluidic techniques for trace element speciation are highlighted.     

Characterization of Novel Aminobenzylcantharidinimides and Related Imides by Proton NMR Spectra and Their Effects on NO Induction

Various acidic anhydrides including cantharidin were converted into corresponding aminobenzylcantharidinimide 3a and analogous imides 3b～k (at the ortho, meta, and para positions) with 35%～87% yields by reacting with aminobenzylamines and triethylamine. The two methyl side chains of cantharidinimides 3ao , 3am , and 3ap, and related imides had more than two chiral centers; the lone pair of electrons of nitrogen displayed a different chemical shift and coupling constant in H‐NMR spectra when the amino group of benzylamine was in the ortho position. These cantharidinimides had parent aniline, pyridine, and naphthalene plane structures, and the primary amine nucleophilicity and basicity might reflect the inductive electron’s negative effect on chemical shifts. We prepared cantharidinimides by heating the reactants cantharidin 1a , aliphatic and aromatic acid anhydrides, primary benzylic amines, and aniline derivatives to ca. 200 °C with 3 mL of dry toluene, and 1～2 mL of triethylamine in high‐pressure sealed tubes (Buchi glasuster 0032) to produce cantharidinimides and their analogues in good yields. The para‐aminobenzylic imides showed greater inhibition of nitric oxide (NO) synthesis by NO synthase (NOS) than did ortho‐ and meta‐aminobenzylic imides. Compound 3fp , para‐aminobenzylic norbonane‐imide, had the most potent effect on inducible NOS among the tested compounds and showed 35% inhibition.     

The effect of friction reduction in the presence of in-plane vibrations

A reduction of friction by vibrations has been observed in various experiments. This effect can be applied to actively control frictional forces by modulating vibrations. Moreover, common methods of controlling friction rely on lubricants and suitable material combinations. The superimposition of vibrations can further reduce the friction force. This study presents a theoretical approach based on the Dahl friction model that describes the friction reduction observed in the presence of the tangential vibrations at an arbitrary angle. Analysis results indicated that the tangential compliance should be considered in modeling the effect of vibrations in reducing friction. At any vibration angle, the tangential compliance of the contacts reduces the friction reduction effect. The vibrations parallel to the macroscopic velocity are most effective for friction reduction.     

EDL configuration on a dissimilarly charged protrusion array via double Fourier series and perturbation method

In this study, through the extension of an one-dimensional, dissimilarly charged protrusions surface model set up in our previous work, a novel dissimilarly charged protrusion array (DCPA) model immersed in an electrolyte solution, which could simulate realistically both the surface morphology and the surface charged condition profoundly concerned on a biological cell membrane, or on the surface of a micro-scale, modified particle used in biomedical engineering and water treatment, is proposed. Considering the condition of small protrusions, the electrical potential field due to the electrical double layer (EDL) on DCPA model is solved semi-analytically using both the double Fourier series and the perturbation method. The analysis from the numerical result reveals that, a small, dissimilarly charged protrusion can lead to a steep variation in the local EDL configuration, especially compared with that in the condition when the charged surface is taken roughly as a flat surface using a lumped, mean surface charge density.