Tetrathiophene on Graphite: Molecular Dynamics Simulations

Summary: We describe molecular dynamics simulations of α‐tetrathiophene molecules deposited on a flat graphite substrate, at two different temperatures (300 K and 400 K) and several degrees of coverage (from approximately one to three molecular layers). The simulations employ a modified version of the CFF91 force field, with the torsion parameters tailored on high‐level ab initio calculations on 2,2′‐bithiophene. We found that the molecules in the first layer were relatively planar and packed against the underlying surface, while those outside it were not arranged in well‐defined layers and were more conformationally disordered. On the time scale of the simulation, the molecules did not crystallize but rather achieved a liquid crystalline‐like state with their average director parallel to the surface.

Side view of the final configuration in the simulation of 24 tetrathiophenes at 300 K. Molecules are depicted with different shades of gray according to their z coordinate (first, second or third layer).     

Deconvolution of Molecular Weight Distributions Using Dynamic Flory‐Schulz Distributions

Summary: The deconvolution of molecular weight distributions (MWDs) may be useful for obtaining information about the polymerization kinetics and properties of catalytic systems. However, deconvolution techniques are normally based on steady‐state assumptions and very little has been reported about the use of non‐stationary approaches for the deconvolution of MWDs. In spite of this, polymerization reactions are often performed in batch or semi‐batch modes. For this reason, dynamic solutions are proposed here for simple kinetic models and are then used for deconvolution of actual MWD data. Deconvolution results obtained with dynamic models are compared to deconvolution results obtained with the standard stationary Flory‐Schulz distributions. For coordination polymerizations, results show that dynamic MWD models are able to describe experimental data with fewer catalytic sites, which indicates that the proper interpretation of the reaction dynamics may be of fundamental importance for kinetic characterization. On the other hand, reaction dynamics induced by modification of chain transfer agent concentration seem to play a minor role in the shape of the MWD in free‐radical polymerizations.

This Figure illustrates that MWDs obtained at unsteady conditions should not be deconvoluted with standard steady‐state Flory‐Schulz distributions.     

Simulation of Amorphous Nylon 6 Using SuSi,a Strategy Based on Generation–Relaxation Algorithms

Summary: The ability of SuSi to generate microstructures of polymers with hydrogen bonding interactions has been checked. This is a random procedure recently developed to localize independent minima. Calculations were performed on nylon 6, a large number of equilibrated and relaxed atomistic models, i.e. microstructures without torsional strain and atomic overlaps, being generated. Results indicated that the generation algorithm implemented in SuSi underestimates the amount of amide groups involved in hydrogen bonding interactions. This is an expected result since no specific criterion was introduced in it to facilitate the formation of specific interactions. Several modifications have been introduced in the generation algorithm to overcome this limitation. The changes induced by these modifications in the generated microstructures are discussed.

A new computational strategy denoted SuSi generates atomistic models of hydrogen bond forming polymers with very reliable results.     

Mathematical Modelling and Computer Simulation of Linear Polymer Degradation: Simple Scissions

Summary: Degradation of a polymer in a reactor by the degrading agent(s) follows a distinct pattern, primarily influenced by structural integrity and reactor environment. This distinct pattern is recorded in the changes in the evolved molecular weight distribution (MWD) or polymer chain length distribution (PCLD) curve characteristics from the initial intact state. Modern size exclusion chromatography (SEC) is the best laboratory‐based method that can clearly provide these plots in the form of chromatogram; however, detailed molecular information is not available. The nature of molecular destruction can be well‐characterised if the distinct MWD shift patterns can be simulated to fingerprint the different chain scission dynamics. This is investigated by our current research using the power of computer simulation techniques to gain insight into the polymer ageing processes. One such technique for studying simple decay processes is presented here, and the results are compared with experimental findings. The concept of a binary tree scission model is introduced to show chain rupture as a sequence of probabilistic events and as a non‐linear function of time. Two new mathematical algorithms, an iterative Monte Carlo structured probability scheme and a semi‐iterative algebraic exact statistical formulation method, are investigated to implement this model and simulate the evolution of resultant temporal MW distribution. The latter, an innovative approach to mathematical modelling, has the potential to generate a statistically perfect instant MWD decay curve. A statistical comparison of the product yield is presented from the data obtained using a wide variety of simulated scission regimes to determine the sources of variability.

Simulated MWD lateral shift for percent cut scission model showing deviation from the initial MWD (red) over degradation time zones T_j(0 ≥ j ≤ 9) with bimodal and curve broadening effect due to accumulation of varied percent cut range 5–30%.     

Simulation of Nanoparticle Production in Premixed Aerosol Flow Reactors by Interfacing Fluid Mechanics and Particle Dynamics

The interaction of fluid mechanics and particle dynamics at the very early stages of flame synthesis largely affects the characteristics of the product powder. Detailed simulations provide a better understanding of these processes, which take place in a few milliseconds, and offer the possibility to influence the product characteristics by intelligent selection of the process parameters. The present paper reports on the simulation of titania powder formation by TiCl₄ oxidation in an aerosol flow reactor. A commercially available fluid mechanics code is used for the detailed calculation of the fluid flow and the chemical reaction at non-isothermal conditions. This code is then interfaced with a model for aggregate particle dynamics neglecting the spread of the particle size distribution. The simulation shows the onset of the particle formation in the reactor and calculates the dynamic evolution of the aggregate particle size, number of primary particles per aggregate and the specific surface area throughout the reactor. The presented, newly developed calculation technique allows for the first time the simulation of particle formation processes under the authentic, complex conditions as found in actual aerosol reactors.     

A comparative study on the modeling of sound pressure field distributions in a sonoreactor with experimental investigation

In sonochemical reactors the effect of emerging cavitation bubbles has significant influence on the amplitude and structure of the developing sound field. Calculations show that the damping parameter and the phase velocity may, depending on the pressure amplitude, change by several orders of magnitude. For example, the sound velocity in water comes to 1500 ms⁻¹, whereas in a bubbly liquid it may decrease to 20 ms⁻¹, which is much below the velocity of sound in air (about 340 ms⁻¹). In this paper, a method of calculating the time dependent three-dimensional pressure field in sonochemical reactors of various shapes is presented. It takes into account inhomogeneous distributed wave parameters which are a function of the spatial depending pressure amplitude. The modeled results are then compared with experimentally measured values of a certain kind of reaction vessel. The agreement is found to be satisfactory.     

基于BP网络和RBF网络的模糊系统建模

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一种有限元模型动力缩聚移频迭代法

提出了一种基于矩阵广义逆的有限元模型动力缩聚移频迭代方法,该方法首先直接从原系统特征方程出发,导出反映系统主,副自由度之间位移关系的动力缩聚矩阵的控制方程,然后给出了相应的迭代求解方法和收敛准则。为了减少求矩阵广义逆的计算工作量,本文给出了一种替代方法,把对一个高阶满阵求逆转化为对一个同阶高度稀疏矩阵求逆。与已有的动力缩聚迭代法相比,本文提出的方法具有两个显著的优点：其一是迭代收敛速度高,其二是通     

基于逆迭代法的结构动力缩聚技术

有限元模型的动力缩聚法已被广泛地应用到大阶系统的特征分析、试验－分析模型的相关分析等领域中。本文从逆迭代法出发,导出了一种有限元模型动力缩聚迭代方法。该方法具有三个显著的优点：其一是收敛速度远远超过现有的动力缩聚迭代法;若干是该迭代法收敛的可以从理论上得到保证,其三是由于没有必要的在每次迭代中都去计算降阶系数的刚度矩阵、质量矩阵和特征问题,因而可减少计算工作量,尤其在主自由度数较大的情况下。     

Identifiability of kinetic models of isotope transient tracing in fixed bed plug flow reactors

A novel method is presented to address the identifiability of a class of kinetic models of monoatomic isotope transient tracing in plug flow reactors. It is shown that the identifiability of these models can be addressed solely from a knowledge of the rate functions. Dedicated to Professor Pál Tétényi on the occasion of his 70th birthday