Viscoelastic behaviour of silica filled natural rubber composites – Correlation of shear with elongational testing

Dynamic mechanical behaviour of natural rubber-silica composites was studied by a frequency sweep method at different temperatures (40 °C,70 °C and 100 °C) using a dynamic mechanical analyzer and a rotorless rheometer, RPA, in an attempt to establish a correlation between the two. The composites with silica content up to 40 phr were studied. It was found that the dependence of dynamic modulus on the frequency as obtained from both the instruments followed a similar trend. This suggests that the dynamic mechanical properties of rubber compounds can be determined even during curing. A correlation could be arrived at between the two sets of data, making it possible to predict one set knowing the other. The impact of silane coupling agent, bis (3-triethoxysilylpropyl tetrasulphide), TESPT, on viscoelasticity was also investigated. The mechanical properties were improved in the presence of TESPT. Additionally, an increase in thermal stability was also observed in the presence of TESPT. Scanning electron micrographs showed the better filler dispersion in the case of silane-coupled silica composites.     

Theoretical approaches for predicting the color of rigid dyes in solution

Aiming at developing an affordable and easily implementable computational protocol for routine prediction of spectral properties of rigid molecular dyes, density functional theory, and time‐dependent density functional theory were used in conjunction with a vibronic coupling scheme for band shape estimate. To predict the perceived color of molecules in solution, a model has been setup linking the UV‐vis spectra predicted at ab initio level to the L *a *b * colorimetric parameters. The results show that a mixed protocol, implying the use of a global hybrid functional for the prediction of adiabatic energy differences and a range separated hybrid for the prediction of potential energy curvature, allows perceived colors to be quantitatively predicted, as demonstrated by the comparison of L *a *b * colorimetric parameters obtained from computed and experimental spectra. © 2017 Wiley Periodicals, Inc.     

A full‐pivoting algorithm for the Cholesky decomposition of two‐electron repulsion and spin‐orbit coupling integrals

A significant reduction in the computational effort for the evaluation of the electronic repulsion integrals (ERI) in ab initio quantum chemistry calculations is obtained by using Cholesky decomposition (CD), a numerical procedure that can remove the zero or small eigenvalues of the ERI positive (semi)definite matrix, while avoiding the calculation of the entire matrix. Conversely, due to its antisymmetric character, CD cannot be directly applied to the matrix representation of the spatial part of the two‐electron spin‐orbit coupling (2e‐SOC) integrals. Here, we present a computational strategy to achieve a Cholesky representation of the spatial part of the 2e‐SOC integrals, and propose a new efficient CD algorithm for both ERI and 2e‐SOC integrals. The proposed algorithm differs from previous CD implementations by the extensive use of a full‐pivoting design, which allows a univocal definition of the Cholesky basis, once the CD δ threshold is made explicit. We show that is the upper limit for the errors affecting the reconstructed 2e‐SOC integrals. The proposed strategy was implemented in the ab initio program Computational Emulator of Rare Earth Systems (CERES), and tested for computational performance on both the ERI and 2e‐SOC integrals evaluation. © 2017 Wiley Periodicals, Inc.     

铜催化苯硼酸与苯并呋咱-1-氧化物的胺化反应

C-N键普遍存在于药物和有机功能分子中,传统构建C-N键的方法包括Goldberg反应、Buchwald-Hartwig偶联、Chan-Lam偶联和C-H键活化胺化.虽然这些方法都可以高效构建C-N键,但它们需要使用官能化的芳基底物、官能化的胺化试剂或在氧化条件下进行.理想的胺化反应应在氧化还原中性条件下进行,更为理想的则是在引入氨基的同时引入另外一个官能团.实现这个目标最直接的策略就是使用氮杂环,通过N-E(E=N或O)键的断裂,N原子和E原子可同时被引入.最近我们课题组利用氨茴内酐和氮杂苯并降冰片烯的C-H键活化反应成功实现了这种双官能团化.尽管该法很有吸引力,但是要通过氮杂环的断裂实现双官能团化,需要发生非张力环的开环,这在热力学上是非常不利的.苯并呋咱-1-氧化物可以开环得到邻二硝基苯中间体.基于对胺化反应的兴趣,我们推测苯并呋咱1-氧化物可以作为一个胺化试剂实现苯硼酸的胺化.尽管亚硝基苯对芳基硼酸进行简单的胺化已经被报道,但需要化学计量的铜盐,或是引入还原剂.因此本文报道铜催化的苯硼酸的胺化反应,该反应以苯并呋咱1-氧化物为胺化试剂,在温和及氧化还原中性条件下成功实现了双官能团化.本文共完成了31个不同官能团取代的硝基苯胺骨架结构的合成,反应均以中等到良好的收率得到目标产物,最高收率可达99%.为了增加反应的实用性,我们还进行了放大实验,实验表明,当苯并呋咱-1-氧化物的量由0.2 mmol放大至4 mmol时,反应仍能以较高的收率得到目标产物.此外,目标产物通过进一步的衍生化反应还可方便地转化为其他杂环类化合物.例如,在PPh3作用下,通过还原环化作用可生成吩嗪.在钯催化下可发生分子内碳氢键氧化反应得到咔唑类化合物.通过还原及重氮化反应还可方便地转化为苯并三唑.总之,我们以苯并呋咱-1-氧化物为胺化试剂,在铜催化下成功实现了苯硼酸的胺化反应,合成了一系列双官能团化产物.该催化体系反应条件温和,底物适用范围广,对各种官能团具有很好的兼容性.     

Progress in thermal-mechantical effects induced by laser

对激光辐照诱导的热与力学问题研究进展进行了综述,包括材料在高温、高升温速率下的本构关系,典型薄板和柱壳等结构在激光辐照下的热力破坏效应,多层材料体系的激光破坏行为等几个方面,并着重介绍了包含相变与烧蚀过程的激光破坏分析模型与机制研究,激光辐照效应的流-热-固耦合数值模拟方法,以及短脉冲激光引起的冲击与破坏机理等方面的研究新进展.     

Structural modeling of beams on elastic foundations with elasticity couplings

A new simplified structural model and its governing equations for beams on elastic foundations with elastic coupling are proposed. This modeling system is simple but appropriate for the initial structural design of large-scale submerged floating-beam structures moored by tension legs spaced at uniform interval along the beam. The model is actually for beam on discrete elastic supports rather than on continuous elastic foundations. Therefore, the governing equations are based on finite difference calculus and solutions for beams on discrete elastic supports with elasticity coupling are also proposed. To clarify the applicability limit of the proposed model, the equivalence between a beam on discrete elastic supports and that on continuous elastic foundation is investigated by comparisons of characteristic solutions.     

Coupled modeling of damage growth and permeability variation in brittle rocks

This paper presents a coupled model for anisotropic damage and permeability evolution by using a micro–macro approach. The damage state is represented by a second order tensor. The evolution of damage is determined from a crack propagation criterion. The free enthalpy function of cracked material is obtained by using micromechanical considerations. It is assumed that cracks exhibit normal aperture which is coupled with the crack growth due to asperities of crack faces. By using Darcy’s law for macroscopic fluid flow and assuming laminar flow in microcracks, the overall permeability of the RVE is obtained by a volume averaging procedure taking into account crack aperture in each orientation.     

A coupled zigzag theory for the dynamics of piezoelectric hybrid cross-ply plates

A recently developed coupled third-order zigzag theory for the statics of piezoelectric hybrid cross-ply plates is extended to dynamics. The theory combines a third-order zigzag approximation for the in-plane displacements and a sub-layerwise linear approximation for the electric potential, considering all components of the electric field. The nonuniform variation of the transverse displacement due to the piezoelectric field is accounted for. The conditions for the absence of shear traction at the top and bottom surfaces and continuity of transverse shear stresses in the presence of electromechanical loading are satisfied exactly, thereby reducing the number of displacement variables to five, which is the same as in a first- or third-order equivalent single-layer theory. The governing equations of motion are derived from the extended Hamilton's principle. The theory is assessed by comparing the Navier solutions for the free and forced harmonic vibration response of simply supported plates with the exact three-dimensional piezoelasticity solutions. Comparisons for hybrid test, composite and sandwich plates establish that the present theory is quite accurate for the dynamic response of moderately thick plates.     

Continuum thermodynamic formulation of models for electromagnetic thermoinelastic solids with application in electromagnetic metal forming

The purpose of this work is the formulation and application of a continuum thermodynamic approach to the phenomenological modeling of a class of engineering materials which can be dynamically formed using strong magnetic fields. This is carried out in the framework of a thermodynamic, internal-variable-based formulation in which the deformation, temperature and magnetic fields are in general coupled. This coupling takes the form of the Lorentz force as an additional supply of momentum, and the electromotive power as an additional supply of energy, in the material. In the current approach, the basic thermomechanical field relations for mass, momentum and moment of momentum are obtained from the total energy balance via invariance, and completed by Maxwells field equations. The constitutive formulation is based on the exploitation of the Müller-Liu entropy principle, here for the case of isotropic thermoelastic, viscoplastic material behaviour. The resulting reduced constitutive and field relations and restrictions are then applied to the modeling and simulation of high-speed electromagnetic forming of metal tubes and sheet metal. In this context, scaling arguments show that, over the relevant length- and timescales of engineering interest, the evolution of the magnetic field is diffusive in nature, and thermal conduction is negligible. Comparison of the simulation and experimental results for the final sheet metal form shows very good agreement.Received: 16 March 2004, Accepted: 6 May 2004, Published online: 17 September 2004PACS: 46.05. + b, 46.25.Hf, 46.35 + z Correspondence to: B. Svendsen