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21.
Dynamic surface elasticity of polymer solutions 总被引:1,自引:0,他引:1
B. A. Noskov 《Colloid and polymer science》1995,273(3):263-270
The surfaces of surfactant solutions exhibit viscoelastic dilational behavior which may be investigated by modern optical and mechanical methods. The present study focuses on the dynamic dilational properties of the polymer solution — gas interface. Linear flexible polymer chains at the surface are considered as consisting of trains, lying on the surface, and loops and tails that protrude into the liquid. The Rouse model is used to describe the inner dynamics of the trains, whereas their motion relative to their neighbors on the surface can be described with the help of the reptation conception. An expression for the complex dynamic dilational surface elasticity has been derived. Although, in general, the relaxation of the surface tension is characterized by an infinite series of relaxation times, it is shown that for many systems the dynamics of the surface layer can be described approximately by only two main relaxation times. The dispersion equation, which was obtained earlier for solutions of conventional surfactants, is shown to be fulfilled for polymer solutions also. 相似文献
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The thermal properties, i.e., heat capacity, enthalpy, entropy, and Gibbs function, and the transition behavior of the copolymer system of 4-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid have been studied based on differential scanning calorimetry. The heat capacities of the glass, crystal, and anisotropic melt are shown to be largely additive on a molar basis. Additivity is lost in the two transition regions, glass transition and disordering transition. Isothermal crystallization experiments on the copolymers revealed the existence of two types of crystals which melt at high temperature (fast-grown crystals) and low temperature (slowly grown crystals). The ATHAS computation method is used to bring heat capacities of the solid state into agreement with approximate frequency spectra. The changes in heat capacity at the glass transitions occur at 434°K for the poly(oxy-1,4-benzoyl) [33.2 J/(K mol)] and at 420°K for poly(oxy-2,6-naphthoyl) [46.5 J/(K mol)]. The copolymers have a transition range of above 100°K. The anisotropic melt is linked to the well-known condis state of poly(oxy-1,4-benzoyl) by a continuous changes in disorder and mobility without an additional first-order transition. 相似文献
24.
The influence of the vapors ofn-amyl orn-decyl alcohol on the stability of single thin liquid films, single bubbles, and foam columns was determined. It was found that the presence of surfactant vapors lowered the stability of foams and single foam films. The mechanism of the destabilizing action of the surfactant vapors on wet, dynamic foams under dynamic conditions is discussed. It is shown that the destabilizing action of the surfactant vapors is a further indication that surface elasticity forces are the main factor determining stability of wet, dynamic foams. 相似文献
25.
Eni Kume Nicolas Martin Peter Dunne Patrick Baroni Laurence Noirez 《Molecules (Basel, Switzerland)》2022,27(22)
Mesoscopic shear elasticity has been revealed in ordinary liquids both experimentally by reinforcing the liquid/surface interfacial energy and theoretically by nonextensive models. The elastic effects are here examined in the frame of small molecules with strong electrostatic interactions such as room temperature ionic liquids [emim][Tf2N] and nitrate solutions exhibiting paramagnetic properties. We first show that these charged fluids also exhibit a nonzero low-frequency shear elasticity at the submillimeter scale, highlighting their resistance to shear stress. A neutron scattering study completes the dynamic mechanical analysis of the paramagnetic nitrate solution, evidencing that the magnetic properties do not induce the formation of a structure in the solution. We conclude that the elastic correlations contained in liquids usually considered as viscous away from any phase transition contribute in an effective way to collective effects under external stress whether mechanical or magnetic fields. 相似文献
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基于线弹性体本构方程系数矩阵的对称性,提出了其对应的逆命题问题,即若材料本构方程是线性且对称的,能否由此确定物体是完全弹性的?论文通过构造势函数的方法对该问题给出了肯定的回答,从而论证了对于符合线性本构关系的材料,其本构方程的对称性与物体的完全弹性相互蕴含,因而是相互等价的. 相似文献
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基于考虑了悬垂链的橡胶弹性统计模型,通过引入应变放大因子,建立了硅橡胶纳米复合材料的基于微观机制的本构关系,其中利用硅橡胶分子信息(分子量M、乙烯基含量wt_(Vi)%)、乙烯基反应程度(q)估算获得本构方程中的交联点间链段分子量(Mc),网络链(network strands)体积分数(Φ)等参数,通过拟合确定了与纳米粒子相关的部分参数(初始应变放大因子X_0,极限应变放大因子X_∞,衰减因子z),对掺杂白炭黑的单组分及长短链配合硅橡胶拉伸应力-应变数据进行拟合,在采用相同X_∞,z值情形下,拟合曲线仍能与实测值符合较好(拟合的Adj.R-Square值分别为0.99576、0.99596)。基于微观物理机制的本构关系能够成为联系微观分子结构参数与宏观应力的桥梁,本文工作有望为更有针对性地改进和优化硅橡胶的性能提供依据。 相似文献
30.
A thermodynamically consistent, large-strain, multi-phase field approach (with consequent interface stresses) is generalized for the case with anisotropic interface (gradient) energy (e.g. an energy density that depends both on the magnitude and direction of the gradients in the phase fields). Such a generalization, if done in the “usual” manner, yields a theory that can be shown to be manifestly unphysical. These theories consider the gradient energy as anisotropic in the deformed configuration, and, due to this supposition, several fundamental contradictions arise. First, the Cauchy stress tensor is non-symmetric and, consequently, violates the moment of momentum principle, in essence the Herring (thermodynamic) torque is imparting an unphysical angular momentum to the system. In addition, this non-symmetric stress implies a violation of the principle of material objectivity. These problems in the formulation can be resolved by insisting that the gradient energy is an isotropic function of the gradient of the order parameters in the deformed configuration, but depends on the direction of the gradient of the order parameters (is anisotropic) in the undeformed configuration. We find that for a propagating nonequilibrium interface, the structural part of the interfacial Cauchy stress is symmetric and reduces to a biaxial tension with the magnitude equal to the temperature- and orientation-dependent interface energy. Ginzburg–Landau equations for the evolution of the order parameters and temperature evolution equation, as well as the boundary conditions for the order parameters are derived. Small strain simplifications are presented. Remarkably, this anisotropy yields a first order correction in the Ginzburg–Landau equation for small strains, which has been neglected in prior works. The next strain-related term is third order. For concreteness, specific orientation dependencies of the gradient energy coefficients are examined, using published molecular dynamics studies of cubic crystals. In order to consider a fully specified system, a typical sixth order polynomial phase field model is considered. Analytical solutions for the propagating interface and critical nucleus are found, accounting for the influence of the anisotropic gradient energy and elucidating the distribution of components of interface stresses. The orientation-dependence of the nonequilibrium interface energy is first suitably defined and explicitly determined analytically, and the associated width is also found. The developed formalism is applicable to melting/solidification and crystal-amorphous transformation and can be generalized for martensitic and diffusive phase transformations, twinning, fracture, and grain growth, for which interface energy depends on interface orientation of crystals from either side. 相似文献