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).     

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%.     

Modeling Microbial Transport and Biodegradation in a Dual-porosity System

A mathematical model describing microbial transport and growth in a heterogeneous aquifer domain, composed of overlapping subdomains of high-permeability and low-permeability materials, is developed. Each material is conceptually visualized as a continuum which occupies the entire considered spatial aquifer domain. Based on the assumption that advection in the low-permeability domain is negligible, the mathematical model is solved by using a publically available reactive transport code. The importance of modeling microbial transport and growth in such a dual-porosity system is demonstrated through a hypothetical case study.     

三维光学数字像的一种解析逼近模型

利用双三次均匀Ｂ样条曲面片建立三维光学数字图像的逼近模型。该数学模型是依据双三次均匀Ｂ样条曲面片对三维光学数字图像的分片逼近技术来建立的。言语中给出了空间自由表面的双三次均匀Ｂ样条表达方法和三维数字像的Ｂ样条重构结果。     

Thermodynamics of polymer systems

This work gives an introduction into the thermodynamic modeling of polymer systems. After a short overview about the different basics of thermodynamic models, results obtained with the recently proposed PC-SAFT equation of state are discussed exemplarily for systems containing polymers as well as copolymers.     

A deforming-mesh finite-element approach applied to the large-translation and free-surface scenario of fused deposition modeling

A numerical study of the fused deposition modeling (FDM) process using a boundary-conforming free-surface finite element approach is performed. Due to the complexity of the FDM process, among all of its parts, we focus on the deposition and spreading of an individual filament. The polymer behavior, that is, the shear rate dependent and temperature-dependent viscosity, is included by the Cross-WLF viscosity model. The moving domain is addressed by the virtual region mesh update method, which, in the present article, is extended to free-surface problems. The particularity of dividing the mesh domain into an activated and a deactivated domain makes it possible to handle large translatory mesh deformation. In this work, we make use of the level of detail offered by a boundary-conforming approach regarding both topology accuracy and the imposition of boundary conditions in order to study the deposition of a single filament at a small scale. Parameters with a direct impact on the mechanical properties of the final object can be straightforwardly computed by a boundary-conforming approach, for instance, the cross-section, the contact area, the temperature distribution, and the heat fluxes over the surfaces. The presented approach is validated by a two-dimensional benchmark test case before the numerical results of the three-dimensional simulation of the filament deposition are shown.     

Modeling of Mechanical Properties of Polymeric Systems with Branching/Crosslinking,Particularly Their Mechanical Resistence and Stability

A theoretical method for the estimation of mechanical characteristics of polymeric structures is proposed. This method uses the statistical polymer method for modeling branched/crosslinked structures. The proposed method is utilized for the estimation of mechanical resistance and stability of microporous polymeric materials. An engineering method for the evaluation of mechanical stability and resistance of polymeric materials is derived.     

Radiative Heat Transfer in a Resistance Heated Floating Zone Furnace: A Numerical Study with FIDAPTM

This paper presents a numerical study of radiative heat transfer in a floating zone (FZ) furnace which was performed by using the commercial finite element program FIDAP^TM. This resistance furnace should provide a temperature higher than the melting temperature of silicon (i.e. T_max ≈ 1500 °C) and a variable temperature gradient at the liquid/solid interface (≥ 25 K/cm). Due to the high working temperatures, heat radiation plays the dominant role for the heat transfer in the furnace. For this reason, the quality of view factors used in the wall‐to‐wall model was carefully inspected with energy‐balance checks. A numerical model with two control parameters is applied to study the influence of material and geometrical parameters on the temperature field. In addition, this model allows us to estimate the internal thermal conditions which were used as thermal boundary conditions for partial 3D simulations. The influences of an optical lens system on the radial symmetry of the temperature field were examined with these partial 3D simulations. Furthermore, we used the inverse modeling method to achieve maximum possible temperature gradients at the liquid/solid interface according to the limitation of maximum available power and the maximum stable height of a melt zone.     

Plasmapolymerisierte Organosilane – Photolumineszenz,Infrarotabsorption und Struktur

Plasma Polymerized Organosilanes – Photoluminescence, Infrared Absorption and Structure The structure of amorphous hydrogen‐containing silicon‐carbon thin films (a‐Si_1–xC_x : H) is difficult to access as known for disordered materials. In this paper we attempt to develop structure models for a‐Si_1–xC_x : H from photoluminescence and infrared transmission, and to support these models through molecular dynamic and LCAO calculations. The modelling is further based on the knowledge of the starting materials in the plasma.