Fluid mechanics revisited

Öttinger's recent nontraditional incorporation of fluctuations into the formulation of the friction matrix appearing in the phenomenological GENERIC theory of nonequilibrium irreversible processes is shown to furnish transport equations for single-component gases and liquids undergoing heat transfer which support the view that revisions to the Navier–Stokes–Fourier (N–S–F) momentum/energy equation set are necessary, as empirically proposed by the author on the basis of an experimentally supported theory of diffuse volume transport. The hypothesis that the conventional N–S–F equations prevail without modification only in the case of “incompressible” fluids, where the density ρ of the fluid is uniform throughout, serves to determine the new phenomenological parameter α^′ appearing in the GENERIC friction matrix. In the case of ideal gases the consequences of this constitutive hypothesis are shown to yield results identical to those derived theoretically by Öttinger on the basis of a “proper” coarse-graining of Boltzmann's kinetic equation. A major consequence of the present work is that the fluid's specific momentum density v is equal to its volume velocity v_v, rather than to its mass velocity v_m, contrary to current views dating back 250 years to Euler. In the case of rarefied gases the proposed modifications are also observed to agree with those resulting from Klimontovich's molecularly based, albeit ad hoc, self-diffusion addendum to Boltzmann's collision integral. Despite the differences in their respective physical models—molecular vs. phenomenological—the role played by Klimontovich's collisional addition to Boltzmann's equation in modifying the N–S–F equations is noted to constitute a molecular counterpart of Öttinger's phenomenological fluctuation addition to the GENERIC friction matrix. Together, these two theories collectively recognize the need to address multiple- rather than single-encounter collisions between a test molecule and its neighbors when formulating physically satisfactory statistical–mechanical theories of irreversible transport processes in gases. Overall, the results of the present work implicitly support the unorthodox view, implicit in the GENERIC scheme, that the translation of Newton's discrete mass-point molecular mechanics into continuum mechanics, the latter as embodied in the Cauchy linear momentum equation of fluid mechanics, cannot be correctly effected independently of the laws of thermodynamics. While Öttinger's modification of GENERIC necessitates fundamental changes in the foundations of fluid mechanics in regard to momentum transport, no basic changes are required in the foundations of linear irreversible thermodynamics (LIT) beyond recognizing the need to add volume to the usual list of extensive physical properties undergoing transport in single-species fluid continua, namely mass, momentum and energy. An alternative, nonGENERICally based approach to LIT, derived from our findings, is outlined at the conclusion of the paper. Finally, our proposed modifications of both Cauchy's linear momentum equation and Newton's rheological constitutive law for fluid-phase continua are noted to be mirrored by counterparts in the literature for solid-phase continua dating back to the classical interdiffusion experiments of Kirkendall and their subsequent interpretation by Darken in terms of diffuse volume transport.     

Extensions of Classical Hydrodynamics

An abstract dynamical system is formulated from three features extracted from classical hydrodynamics. One its particular realization is then the classical hydrodynamics, other possible realizations are extensions of the classical hydrodynamics. The three features entering the formulation of the abstract dynamical system are the conservation laws, the compatibility with equilibrium thermodynamics, and the compatibility with classical mechanics in the limit of no dissipation. The particular extensions on which we illustrate the process of constructing different realizations are those arising when dealing with fluids in the vicinity of gas-liquid phase transitions (i.e. fluids involving large spatial inhomogeneities and large fluctuations).     

The mathematical representation of driven thermodynamic systems

A general framework for the treatment of driven systems in nonequilibrium thermodynamics is discussed for two selected theories and a simple model system. The framework is based upon the of modeling and control of general physical systems proposed by van der Schaft and co-workers. The crucial concept is the notion of a Dirac structure representing the dynamical equations of motion as well as the power conserving interconnection structure of the system. We applied the framework to two existing theories and a very simple model system. The two selected theories are the “General Equation for the Non-Equilibrium Reversible-Irreversible Coupling” (GENERIC) formalism of Grmela and Öttinger and the Matrix model of Jongschaap; the model system is a viscous gas in a cylinder and an externally driven piston. It is shown that the new approach provides not only a common framework for both theories, but also useful extensions, in particular, an extended GENERIC treatment of driven systems.     

纤维悬浮聚合物熔体描述的均一结构多尺度模型

通过对纤维悬浮聚合物熔体的可逆和不可逆热力学过程的耦合,建立了分子链弹性哑铃模型与悬浮纤维取向描述相耦合的、具有均一 (GENERIC) 结构形式的熔体多尺度模型. 由该均一结构的多尺度模型不仅可以得出熔体不同尺度上的应力贡献,还可为一般多尺度模型方程组的建立提供其结构形式均一化的方法. 关键词： GENERIC结构 纤维取向 黏弹性 聚合物     

Fluctuation symmetry leads to GENERIC equations with non-quadratic dissipation

We develop a formalism to discuss the properties of GENERIC systems in terms of corresponding Hamiltonians that appear in the characterization of large-deviation limits. We demonstrate how the GENERIC structure naturally arises from a certain symmetry in the Hamiltonian, which extends earlier work that has connected the large-deviation behavior of reversible stochastic processes to the gradient-flow structure of their deterministic limit. Natural examples of application include particle systems with inertia.     

Thermodynamic admissibility of the pompon model for branched polymers

The pompon model for branched polymers is re-formulated within a general framework of nonequilibrium thermodynamics. While the original model of McLeish and Larson is found to be thermodynamically admissible, nonequilibrium thermodynamics strongly suggests several model modifications. As an immediate consequence, a nonzero second normal-stress coefficient in shear flow is predicted by the modified pompon model. Received: 12 April 2000 Accepted: 11 September 2000     

Theoretical modeling of microstructured liquids: a simple thermodynamic approach

A new method is presented for accounting for microstructural features of flowing complex fluids at the level of mesoscopic, or coarse-grained, models by ensuring compatibility with macroscopic and continuum thermodynamics and classical transport phenomena. In this method, the microscopic state of the liquid is described by variables that are local expectation values of microscopic features. The hypothesis of local thermodynamic equilibrium is extended to include information on the microscopic state, i.e., the energy of the liquid is assumed to depend on the entropy, specific volume, and microscopic variables. For compatibility with classical transport phenomena, the microscopic variables are taken to be extensive variables (per unit mass or volume), which obey convection-diffusion-generation equations. Restrictions on the constitutive laws of the diffusive fluxes and generation terms are derived by separating dissipation by transport (caused by gradients in the derivatives of the energy with respect to the state variables) and by relaxation (caused by non-equilibrated microscopic processes like polymer chain stretching and orientation), and by applying isotropy. When applied to unentangled, isothermal, non-diffusing polymer solutions, the equations developed according to the new method recover those developed by the Generalized Bracket [J. Non-Newtonian Fluid Mech. 23 (1987) 271; A.N. Beris, B.J. Edwards, Thermodynamics of Flowing Systems with Internal Microstructure, first ed., Oxford University Press, Oxford, 1994] and by the Matrix Model [J. Rheol. 38 (1994) 769]. Minor differences with published results obtained by the Generalized Bracket are found in the equations describing flow coupled to heat and mass transfer in polymer solutions. The new method is applied to entangled polymer solutions and melts in the general case where the rate of generation of entanglements depends nonlinearly on the rate of strain. A link is drawn between the mesoscopic transport equations of entanglements and conformation and the microscopic equation describing the configurational distribution of polymer segment stretch and orientation. Constraints are derived on the generation terms in the transport equations of entanglements and conformation, and the formula for the elastic stress is generalized to account for reversible formation and destruction of entanglements. A simplified version of the transport equation of conformation is presented which includes many previously published constitutive models, separates flow-induced polymer stretching and orientation, yet is simple enough to be useful for developing large-scale computer codes for modeling coupled fluid flow and transport phenomena in two- and three-dimensional domains with complex shapes and free surfaces.     

Nonlinear rheological models for structured interfaces

The GENERIC formalism is a formulation of nonequilibrium thermodynamics ideally suited to develop nonlinear constitutive equations for the stress-deformation behavior of complex interfaces. Here we develop a GENERIC model for multiphase systems with interfaces displaying nonlinear viscoelastic stress-deformation behavior. The link of this behavior to the microstructure of the interface is described by including a scalar and a tensorial structural variable in the set of independent surface variables. We derive an expression for the surface stress tensor in terms of these structural variables, and a set of general nonlinear time evolution equations for these variables, coupling them to the deformation field. We use these general equations to develop a number of specific models, valid for application near equilibrium, or valid for application far beyond equilibrium.     

On the rheology of immiscible blends

We propose a family of new models making a direct link between flow and structure for immiscible mixtures of viscoelastic fluids undergoing high deformation flows. The morphology is treated both at local (Doi-Ohta-type) and more macroscopic (droplet-like) scales. The governing equations, that include expressions for the extra stress tensor, agree with the conservation laws and with the observed compatibility with thermodynamics. In the particular case in which only one of the two characterizations of the morphology is used, extended versions of the Doi-Ohta and the Maffettone and Minale models are obtained. The extension consists of involving explicitly the free energy in the governing equations and completing the expressions for the extra stress tensor. Received: 24 January 2001 Accepted: 24 April 2001