有序介孔材料: 历史、 现状与发展趋势

有序介孔材料是指孔径在2~50 nm之间的多孔材料, 是一类具有均匀孔径、 高有序度纳米孔道和高比表面积的新材料. 在过去30年里, 有序介孔材料的研究取得了长足的进步, 在可控合成、 结构设计和调控及功能化等方面形成了系统的理论. 同时, 其应用领域也不断被拓展, 包括能源存储与转化、 催化、 生物医药和传感等方面. 本文首先回顾了有序介孔材料的发展历史, 简要介绍发展过程中“里程碑式”的研究工作; 然后根据构效关系总结了其在不同领域应用的最新进展; 最后讨论了有序介孔材料领域进一步发展所面临的挑战与机遇, 并对未来前景进行了展望.     

石墨炔零价金属原子催化剂的合成及应用

原子催化剂是零价金属原子锚定于载体上的一种新型催化剂, 具有原子利用率高、 选择性高以及反应活性和稳定性高等优点, 一直是催化领域的研究前沿, 在催化和能量转换领域具有广阔的发展前景. 石墨炔与金属原子之间独特的不完全电荷转移性质实现了零价过渡金属原子的稳定锚定, 解决了传统单原子催化剂易迁移和聚集的问题, 被认为是新一代催化剂. 本综述从石墨炔原子催化剂的结构性质、 表征以及应用等方面出发, 综合评述了相关领域的最新研究成果, 介绍了石墨炔原子催化剂在电催化固氮制氨、 产氢、 全水解和CO₂固定等方面的应用和发展前景, 为实现新概念高性能催化材料的设计合成提供了研究思路.     

有机半导体非平衡态HOMO和LUMO能量位移规律与OLED中“热激子”形成的唯象理解

以能斯特方程为基础, 通过分析电流密度与氧化还原物种活度变化, 即载流子浓度变化的关系, 计算出有机半导体材料电极电势的变化, 从而建立起有机半导体前线轨道, 即最高占据分子轨道(HOMO)能级和最低未被占据分子轨道(LUMO)能级相对于热力学平衡态的能量位移随电流密度变化的数学关系. 进而依据能级能量位移引起的能隙变化, 提出了有机电致发光显示器（OLED）中“热激子”的产生机制.     

Energy elastic effects and the concept of temperature in flowing polymeric liquids

The incorporation of energy elastic effects in the modeling of flowing polymeric liquids is discussed. Since conformational energetic effects are determined by structural features much smaller than the end-to-end vector of the polymer chains, commonly employed single conformation tensor models are insufficient to describe energy elastic effects. The need for a local structural variable is substantiated by studying a microscopic toy model with energetic effects in the setting of a generalized canonical ensemble. In order to examine the dynamics of flowing polymeric liquids with energy elastic effects, a thermodynamically admissible set of evolution equations is presented that accounts for the evolution of the microstructure in terms of a slow tensor, as well as a fast, local scalar variable. It is demonstrated that the temperature used in the definition of the heat flux is directly related to the Lagrange multiplier of the microscopic energy in the generalized canonical partition function. The temperature equation is discussed with respect to, first, the dependence of the heat capacity on the polymer conformation and, second, the possibility to measure experimentally the effects of the conformational energy.

Measurement of energy release rate and energy flux of rapidly bifurcating crack in Homalite 100 and Araldite B by high-speed holographic microscopy

High-speed holographic microscopy is applied to take three successive photographs of fast propagating cracks in Homalite 100 or in Araldite B at the moment of bifurcation. Crack speed at bifurcation is about 540 m/s on Homalite 100, and about 450 m/s on Araldite B. From the photographs, crack speeds immediately before and after bifurcation are obtained, and it is found that discontinuous change of crack speed does not exist at the moment of bifurcation in the case of Homalite 100, but exists in the case of Araldite B. From the photographs, crack opening displacement (COD) is also measured along the cracks as a function of distance r from the crack tips. The measurement results show that the CODs are proportional to √r before bifurcation. After bifurcation, the CODs of mother cracks are proportional to √r, though the CODs of branch cracks are not always proportional to √r. The energy release rate is obtained from the measured CODs, and it is found that energy release rate is continuous at bifurcation point in both cases of Homalite 100 and Araldite B. Energy flux that shows the energy flow toward a crack tip is also obtained.     

Energy release rates in a constrained epoxy disc with Hookean and Mooney–Rivlin materials

Assuming that the disc material can be modeled either as Mooney–Rivlin or as Hookean and the steel ring enclosing the disc as Hookean, the energy release rates as a function of the crack length are evaluated and compared. Two loadings are considered––one in which the surface of the star shape hole in the disc is loaded by a uniform pressure and the other in which the temperature of the composite body is uniformly raised. It is found that the linear and the nonlinear analyses give qualitatively similar results for the two loadings. For each load, the energy release rate increases with an increase in the starter crack length, reaches a maximum value and then decreases gradually.     

Analysis of material instabilities in inelastic solids by incremental energy minimization and relaxation methods: evolving deformation microstructures in finite plasticity

We propose an approach to the definition and analysis of material instabilities in rate-independent standard dissipative solids at finite strains based on finite-step-sized incremental energy minimization principles. The point of departure is a recently developed constitutive minimization principle for standard dissipative materials that optimizes a generalized incremental work function with respect to the internal variables. In an incremental setting at finite time steps this variational problem defines a quasi-hyperelastic stress potential. The existence of this potential allows to be recast a typical incremental boundary-value problem of quasi-static inelasticity into a principle of minimum incremental energy for standard dissipative solids. Mathematical existence theorems for sufficiently regular minimizers then induce a definition of the material stability of the inelastic material response in terms of the sequentially weakly lower semicontinuity of the incremental variational functional. As a consequence, the incremental material stability of standard dissipative solids may be defined in terms of the quasi-convexity or the rank-one convexity of the incremental stress potential. This global definition includes the classical local Hadamard condition but is more general. Furthermore, the variational setting opens up the possibility to analyze the post-critical development of deformation microstructures in non-stable inelastic materials based on energy relaxation methods. We outline minimization principles of quasi- and rank-one convexifications of incremental non-convex stress potentials for standard dissipative solids. The general concepts are applied to the analysis of evolving deformation microstructures in single-slip plasticity. For this canonical model problem, we outline details of the constitutive variational formulation and develop numerical and semi-analytical solution methods for a first-level rank-one convexification. A set of representative numerical investigations analyze the development of deformation microstructures in the form of rank-one laminates in single slip plasticity for homogeneous macro-deformation modes as well as inhomogeneous macroscopic boundary-value problems. The well-posedness of the relaxed variational formulation is indicated by an independence of typical finite element solutions on the mesh-size.     

Rate independent hysteresis in a bi-stable chain

The nontrivial behavior of an elastic chain with identical bi-stable elements may be considered prototypical for a large number of nonlinear processes in solids ranging from phase transitions to fracture. The energy landscape of such a chain is extremely wiggly which gives rise to multiple equilibrium configurations and results in a hysteretic evolution and a possibility of trapping. In the present paper, which extends our previous study of the static equilibria in this system (Puglisi and Truskinovsky, J. Mech. Phys. Solids (2000) 1), we analyze the behavior of a bi-stable chain in a soft device under quasi-static loading. We assume that the system is over-damped and explore the variety of available nonequilibrium transformation paths. In particular, we show that the “minimal barrier” strategy leads to the localization of the transformation in a single spring. Loaded periodically, our bi-stable chain exhibits finite hysteresis which depends on the height of the admissible barrier; the cold work/heat ratio in this model is a fixed constant, proportional to the Maxwell stress. Comparison of the computed inner and outer hysteresis loops with recent experiments on shape memory wires demonstrates good qualitative agreement. Finally we discuss a relation between the present model and the Preisach model which is a formal interpolation scheme for hysteresis, also founded on the idea of bi-stability.     

Preliminary report on the energy balance for nonlinear oscillations

In this paper, a reliable technique for calculating angular frequencies of nonlinear oscillators is developed. The new algorithm offers a promising approach by constructing a Hamiltonian for the nonlinear oscillator. Some illustrative examples are given.     

Analysis of energy release rate for composite delaminated cylindrical shells subjected to axial compression

In this paper, the postbuckling governing equations and the analytical expression of the energy release rates associated with delamination growth in a compression-loaded cylindrical shell are derived by using the variational principle of moving boundary and the Griffith fracture criterion. The finite difference method is used to generate the postbuckling solutions of the delaminated cylindrical shells, and with these solutions, the values of the energy release rates are determined. In simulational examples, the effects of a wide range of parameters, such as delamination sizes and depths, boundary conditions, geometrical parameters, material properties and laminate stacking sequences on the energy release rates of axisymmetrical laminated cylindrical shells are intensively discussed.The English text was polished by Yunming Chen.