峨山褐煤的分子结构和分子模拟

作为重要的化石能源，褐煤资源潜力巨大、分布广泛但综合利用率低。研究褐煤的分子结构模型，有助于预测褐煤在热解、液化和气化过程中的化学反应机理及反应路径，进而提高褐煤的综合应用水平。以云南峨山褐煤为研究对象，利用傅里叶变换红外光谱、13C核磁共振波谱及X射线光电子能谱等分析测试方法，获取了峨山褐煤的含碳、含氧及含氮结构参数。在此基础上，借助Gaussian 09计算平台，采用量子化学建模的方法构建并优化了峨山褐煤的分子结构模型。研究结果表明：峨山褐煤的芳碳率为39.20%，芳香碳结构主要为苯和萘，且芳香桥头碳与周边碳的比值χ_b为0.07；脂碳率为49.51%，脂肪碳结构主要为亚甲基，季碳和氧接脂碳；氧原子主要存在于羟基、醚氧、羰基和羧基结构中；含氮结构则以吡啶为主。基于元素分析、13C 核磁共振波谱分析，又经过热重实验消除褐煤中残余水分的影响后，计算出峨山褐煤的分子式为C₁₅₃H₁₃₇O₃₅N₂。依据分子式及分析结果计算出峨山褐煤的结构单元含量并构建出其初始结构模型，采用半经验法PM 3基组及密度泛函理论M06-2X/3-21G基组对初始分子构型进行优化。优化后的分子模型具有明显的三维立体特征，芳香环之间较为分散且在空间中排列不规则，芳香簇主要通过亚甲基、醚氧基、羰基、酯基和脂肪环连接，含氧官能团主要分布在分子边缘，脂肪族侧链较多。对优化后的分子模型进行振动频率计算进而获得了分子模型的模拟红外光谱，其与实验红外谱图吻合度良好，证明了峨山褐煤分子结构模型的准确性、合理性。分子结构模型的构建有利于直观地了解峨山褐煤的分子结构特征，从而有助于从微观分子角度研究峨山褐煤的宏观性质。同时，峨山褐煤分子结构模型可为其在热解、液化和气化等领域研究中提供理论指导。     

染料敏化太阳能电池载流子传输的数值模拟

由于在染料敏化太阳能电池(dye-sensitized solar cell, DSSC)中存在染料弛豫、半导体薄膜中电子与氧化态染料分子发生反应和电子在电解质中与氧化态离子复合等不利反应,利用一个更完善的DSSC载流子传输模型对电池的光电性能进行模拟就显得非常重要。为此,本文基于由多重俘获理论建立的DSSC中的包括电子、染料阳离子、碘化物和三碘化物在内的载流子传输模型,数值模拟得到了不同TiO₂薄膜厚度、不同入射光强度与不同染料分子吸收系数下DSSC的J-V曲线。结果表明,随着TiO₂薄膜厚度的增加,太阳能电池的短路电流密度增大,开路电压减小,光电转换效率先增大后减小。当DSSC的TiO₂薄膜厚度为20 μm时,光电转换效率达到最大值7.41%,同时光电转换效率随入射光强度与染料分子吸收系数的增大均有一定程度提高,其中在吸收系数为4 500 cm^-1时,光电转换效率为6.73%。以上结果可以为改进DSSC的光电性能提供理论指导。     

Numerical simulation of transpiration cooling through porous material

Transpiration cooling using ceramic matrix composite materials is an innovative concept for cooling rocket thrust chambers. The coolant (air) is driven through the porous material by a pressure difference between the coolant reservoir and the turbulent hot gas flow. The effectiveness of such cooling strategies relies on a proper choice of the involved process parameters such as injection pressure, blowing ratios, and material structure parameters, to name only a few. In view of the limited experimental access to the subtle processes occurring at the interface between hot gas flow and porous medium, reliable and accurate simulations become an increasingly important design tool. In order to facilitate such numerical simulations for a carbon/carbon material mounted in the side wall of a hot gas channel that are able to capture a spatially varying interplay between the hot gas flow and the coolant at the interface, we formulate a model for the porous medium flow of Darcy–Forchheimer type. A finite‐element solver for the corresponding porous medium flow is presented and coupled with a finite‐volume solver for the compressible Reynolds‐averaged Navier–Stokes equations. The two‐dimensional and three‐dimensional results at Mach number Ma = 0.5 and hot gas temperature T_HG=540 K for different blowing ratios are compared with experimental data. Copyright © 2014 John Wiley & Sons, Ltd.     

Blended-fuel based EDC combustion model and its application in heptane-ethanol fire simulation

The blended-fuel based eddy-dissipation-concept combustion model was newly developed in the FireFOAM framework, and applied to simulate 30 cm×30 cm heptane-ethanol pool fire. Comparison was made of fire height, centerline temperature against experimental measurements, which shows that they match very well with each other. However, further studies are needed to examine the validation of this model in fire simulations with various scales.     

In Situ Detection of Particle Aggregation on Electrode Surfaces

Partially blocked electrodes (PBEs) are important; many applications use non‐conductive nanoparticles (NPs) to introduce new electrode functionalities. As aggregation is a problem in NP immobilization, developing an in situ method to detect aggregation is vital to characterise such modified electrodes. We present chronoamperometry as a method for detection of NP surface aggregation and semi‐quantitative sizing of the formed aggregates, based on the diffusion limited current measured at PBEs as compared with the values calculated numerically for different blocking feature sizes. In contrast to voltammetry, no approximations on electrode kinetics are needed, making chronoamperometry a more general and reliable method. Sizing is shown for two modification methods. Upon drop casting, significant aggregation is observed, while it is minimized in electrophoretic NP deposition. The aggregate sizes determined are in semi‐quantitative agreement with ex situ microscopic analysis of the PBEs.     

Error Estimates for a Class of Elliptic Optimal Control Problems

In this article, functional type a posteriori error estimates are presented for a certain class of optimal control problems with elliptic partial differential equation constraints. It is assumed that in the cost functional the state is measured in terms of the energy norm generated by the state equation. The functional a posteriori error estimates developed by Repin in the late 1990s are applied to estimate the cost function value from both sides without requiring the exact solution of the state equation. Moreover, a lower bound for the minimal cost functional value is derived. A meaningful error quantity coinciding with the gap between the cost functional values of an arbitrary admissible control and the optimal control is introduced. This error quantity can be estimated from both sides using the estimates for the cost functional value. The theoretical results are confirmed by numerical tests.     

A modified pseudospectral method for solving trajectory optimization problems with singular arc

This paper presents a direct method based on Legendre–Radau pseudospectral method for efficient and accurate solution of a class of singular optimal control problems. In this scheme, based on a priori knowledge of control, the problem is transformed to a multidomain formulation, in which the switching points appear as unknown parameters. Then, by utilizing Legendre‐Radau pseudospectral method, a nonlinear programming problem is derived which can be solved by the well‐developed parameter optimization algorithms. The main advantages of the present method are its superior accuracy and ability to capture the switching times. Accuracy and performance of the proposed method are examined by means of some numerical experiments. Copyright © 2016 John Wiley & Sons, Ltd.     

Effects of awareness program and delay in the epidemic outbreak

In the present paper, an epidemic model has been proposed and analyzed to investigate the impact of awareness program and reporting delay in the epidemic outbreak. Awareness programs induce behavioral changes within the population, and divide the susceptible class into two subclasses, aware susceptible and unaware susceptible. The existence and the stability criteria of the equilibrium points are obtained in terms of the basic reproduction number. Considering time delay as the bifurcating parameter, the Hopf bifurcation analysis has been performed around the endemic equilibrium. The direction of the Hopf bifurcation and the stability of the bifurcating periodic solutions are investigated by using the normal form theory and central manifold theorem. To verify the analytical results, comprehensive numerical simulations are carried out. Copyright © 2016 John Wiley & Sons, Ltd.     

Hybrid projection methods for equilibrium problems with non‐Lipschitz type bifunctions

Based on the extended extragradient‐like method and the linesearch technique, we propose three projection methods for finding a common solution of a finite family of equilibrium problems. The linesearch used in the proposed algorithms has allowed to reduce some conditions imposed on equilibrium bifunctions. The strongly convergent theorems are established without the Lipschitz‐type condition of bifunctions. The paper also helps in the design and analysis of practical algorithms and gives us a generalization of some previously known problems. Copyright © 2017 John Wiley & Sons, Ltd.