A statistical approach to characterize the viscoelastic creep compliances of a vinyl ester polymer

The objective of this study was to develop a model to predict the viscoelastic material functions of a vinyl ester (VE) polymer with variations in its experimentally obtained material properties under combined isothermal and mechanical loading. Short-term tensile creep experiments were conducted at three temperatures below the glass transition temperature of the VE polymer, with 10 replicates for each test configuration. The measured creep strain versus time responses were used to determine the creep compliances using the generalized viscoelastic constitutive equation with a Prony series representation. The variation in the creep compliances of a VE polymer was described by formulating the probability density functions (PDFs) and the corresponding cumulative distribution functions (CDFs) of the creep compliances using a two-parameter Weibull distribution. Both Weibull scale and shape parameters of the creep compliance distributions were shown to be time and temperature dependent. Two-dimensional quadratic Lagrange interpolation functions were used to characterize the Weibull parameters to obtain the PDFs and, subsequently, the CDFs of the creep compliances for the complete design temperature range during steady state creep. At each test temperature, creep compliance curves were obtained for constant CDF values and compared with the experimental data. The predicted creep compliances of the selected VE polymer in the design space are in good agreement with the experimental data for all three test temperatures.     

The Interstitial Carbon of the Nitrogenase FeMo Cofactor is Far Better Stabilized than Previously Assumed

The first quantum-mechanical calculations of all relevant potential constants in both the iron-molybdenum cofactor and the iron-vanadium cofactor of nitrogenase suggest that the carbide is bound to the center of the enzyme much more strongly than hitherto assumed. Previous studies seemed to indicate a dummy function of the interstitial carbon, with a weak force constant (ca. 0.32 N cm⁻¹). Our new investigations confirm a different picture: the central carbon atom binds the iron-sulfur cluster through six covalent C−Fe bonds. With a potential constant of more than 1.3 N cm⁻¹, the interstitial carbon also appears to be dynamically persistent. According to our investigations, the values for the elasticity within the iron-sulfur cluster have to be corrected too. These new details on the mechano-chemical properties of the FeMo cofactor will be important for elucidating the catalytic cycle of nitrogen fixation. By implementing our new algorithm in the freely available COMPLIANCE program, the dependence on the coordinates during the calculation of Hesse matrices is eliminated completely.     

A generalized Duffing equation with the Coulomb’s friction law and Signorini–type contact conditions

This work provides mathematical and numerical analyses for a spring–mass system, in which Signorini–type contact conditions and Coulomb’s friction law with thermal effects are taken into consideration. The motion of a mass attached to a viscoelastic (Kelvin–Voigt type) nonlinear spring is described by a generalized Duffing equation. Signorini contact conditions are understood as extended complementarity conditions (CCs), where convolution is incorporated, allowing to consider thermal aspects of an obstacle. We prove the existence of global weak solutions for the highly nonlinear differential equation system with all the conditions, based on the regularized differential equation and the normal compliance condition with the standard mollifier. In addition, we investigate what side effects produce higher singularities of contact forces in dynamic contact problems, which is also supported by numerical evidences. Numerical schemes are proposed and then several groups of data are selected for the display of our numerical simulations.     

Modelling of flow pattern in a shallow aquifer affected by reservoirs

A compartmental model is developed to estimate flow parameters of a shallow aquifer affected by water loads in surface reservoirs and to evaluate its nonsteady flow distribution. The method incorporates temporal piezometric head measurements and sampling of water for dissolved chemicals and isotopes analyses. Each compartment is governed by a set of equations describing the conservation of linear momentum and mass balance expressions for water, isotopes, and dissolved chemicals. The number of compartmental balance expressions always must be greater than that of the unknown flow parameters associated with each compartment. An optimization method is described to yield spatial distribution of aquifer storativity, transmissivity, porosity, leakage, and compliance coefficients and fluxes leaking into an aquifer's lower boundary. Future predictions of an aquifer's piezometric head distribution in a compartmental system is formulated on the basis of the estimated flow parameters and the leakage components.Compartmental modelling which incorporates concentrations of environmental tracers, may yield efficiency in computing resources and accuracy enhancement for predicting an aquifer's flow regime.     

炮药断裂韧性初探

高膛压炮的问世,对炮药的力学性能提出了更高的要求。本文根据炮药的性质、加工和使用的特点,探讨炮药断裂韧性的测定。     

Quasistatic Viscoelastic Contact with Normal Compliance and Friction

We prove the existence of a unique weak solution to the quasistatic problem of frictional contact between a deformable body and a rigid foundation. The material is assumed to have nonlinear viscoelastic behavior. The contact is modeled with normal compliance and the associated version of Coulomb's law of dry friction. We establish the continuous dependence of the solution on the normal compliance function. Moreover, we prove the existence of a unique solution to the problem of sliding contact with wear. This revised version was published online in August 2006 with corrections to the Cover Date.     

试验确定自增强圆筒的表面裂纹K1因子和疲劳扩展规律

本文提供了一种可以进行自增强处理的圆筒试样,通过实验用柔度法确定了该试样的表面裂纹的应力强度因子,介绍了含表面裂纹试样的柔度测试技术,导出了柔度与表面裂纹尖端前缘各点的应力强度因子的关系式,该式可作为各种含表面裂纹试样柔度法测表面裂纹 K_1因子的参考,本文还测定了不同自增强程度下,自增强圆筒的表面裂纹疲劳扩展规律。     

Influence of long-chain branches in polyethylenes on linear viscoelastic flow properties in shear

 This contribution presents a survey on the influence of long-chain branching on the linear viscoelastic properties zero shear-rate viscosity and steady-state recoverable compliance of polyethylene melts. The materials chosen are linear and slightly long-chain branched metallocene-catalyzed polyethylenes of narrow molecular mass distribution as well as linear and highly long-chain branched polyethylenes of broad molecular mass distribution. The linear viscoelastic flow properties are determined in shear creep and recovery experiments by means of a magnetic bearing torsional creep apparatus. The analysis of the molecular structure of the polyethylenes is performed by a coupled size exclusion chromatography and multi-angle laser light scattering device. Polyethylenes with a slight degree of long-chain branching exhibit a surprisingly high zero shear-rate viscosity in comparison to linear polyethylenes whereas the highly branched polyethylenes have a much lower viscosity compared to linear samples. Slightly branched polyethylenes have got a higher steady-state compliance in comparison to linear products of similar polydispersity, whereas the highly branched polyethylenes of broad molecular mass distribution exhibit a surprisingly low elasticity in comparison to linear polyethylenes of broad molecular mass distribution. In addition sparse levels of long-chain branching cause a different time dependence in comparison to linear polyethylenes. The experimental findings are interpreted by comparison with rheological results from literature on model branched polymers of different molecular topography and chemical composition. Received: 12 July 2001 Accepted: 30 October 2001     

High temperature creep behavior of phosphoric acid‐polybenzimidazole gel membranes

This work investigates the effects of polymer solids content and macromolecular structure on the high temperature creep behavior of polybenzimidazole (PBI) gel membranes imbibed with phosphoric acid (PA) after preparation via a polyphosphoric acid (PPA) mediated sol‐gel process Low‐solids, highly acid‐doped PBI membranes demonstrate outstanding fuel cell performance under anhydrous, ambient pressure, and high temperature (120–200 °C) operating conditions. However, PBI membranes are susceptible to creep under compressive loads at elevated temperatures, so their long‐term mechanical durability is a major concern. Here, we report results for the creep behavior of PBI membranes subject to compression at 180 °C. For para‐ and meta‐PBI homopolymers, increasing polymer solids content results in lower creep compliance and higher extensional viscosity, which may be rationalized by increasing chain density in the sol‐gel network. Comparing various homo‐ and copolymers at similar solids loading, differences in creep behavior may be rationalized in terms of chain–chain and chain‐solvent interactions that control macromolecular solubility and stiffness in the PA solvent. The results demonstrate the feasibility of improving the mechanical properties of PA‐doped PBI membranes by control of polymer solids content and rational design of PBI macromolecular structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1527–1538     

Measurement of viscoelastic properties for polymers by nanoindentation

A new method has been proposed and verified to measure the viscoelastic properties of polymers by nanoindentation tests. With the mechanical response of load–displacement curves at different loading rates, the parameters of creep compliance and relaxation modulus are calculated through the viscoelastic contact model. Dynamic thermomechanical analysis (DMA) tests are conducted to compare the results by the proposed technique. The results show that the correlation coefficients between DMA tests and the new method are above 0.9 in the entire range, which verified the feasibility of the method. The loading curves fitted by the model are identical to the experimental curves within the discrete points and so it shows that this technique is more suitable for general linear viscoelastic materials. Numerical creep tests are carried out to examine the effectiveness of the proposed method by input the Prony series calculated by the three-element Maxwell model and the viscoelastic contact model. The good agreement shows that the proposed technique can be applied in practice.