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1.
J Chem Phys ; 140(7): 074904, 2014 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-24559367

RESUMO

We examine the simplest relevant molecular model for large-amplitude shear (LAOS) flow of a polymeric liquid: the suspension of rigid dumbbells in a Newtonian solvent. We find explicit analytical expressions for the shear rate amplitude and frequency dependences of the first and third harmonics of the alternating shear stress response. We include a detailed comparison of these predictions with the corresponding results for the simplest relevant continuum model: the corotational Maxwell model. We find that the responses of both models are qualitatively similar. The rigid dumbbell model relies entirely on the dumbbell orientation to explain the viscoelastic response of the polymeric liquid, including the higher harmonics in large-amplitude oscillatory shear flow. Our analysis employs the general method of Bird and Armstrong ["Time-dependent flows of dilute solutions of rodlike macromolecules," J. Chem. Phys. 56, 3680 (1972)] for analyzing the behavior of the rigid dumbbell model in any unsteady shear flow. We derive the first three terms of the deviation of the orientational distribution function from the equilibrium state. Then, after getting the "paren functions," we use these for evaluating the shear stress for LAOS flow. We find the shapes of the shear stress versus shear rate loops predicted to be reasonable.

2.
Annu Rev Chem Biomol Eng ; 7: 479-507, 2016 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-27276553

RESUMO

To solve problems in polymer fluid dynamics, one needs the equations of continuity, motion, and energy. The last two equations contain the stress tensor and the heat-flux vector for the material. There are two ways to formulate the stress tensor: (a) One can write a continuum expression for the stress tensor in terms of kinematic tensors, or (b) one can select a molecular model that represents the polymer molecule and then develop an expression for the stress tensor from kinetic theory. The advantage of the kinetic theory approach is that one gets information about the relation between the molecular structure of the polymers and the rheological properties. We restrict the discussion primarily to the simplest stress tensor expressions or constitutive equations containing from two to four adjustable parameters, although we do indicate how these formulations may be extended to give more complicated expressions. We also explore how these simplest expressions are recovered as special cases of a more general framework, the Oldroyd 8-constant model. Studying the simplest models allows us to discover which types of empiricisms or molecular models seem to be worth investigating further. We also explore equivalences between continuum and molecular approaches. We restrict the discussion to several types of simple flows, such as shearing flows and extensional flows, which are of greatest importance in industrial operations. Furthermore, if these simple flows cannot be well described by continuum or molecular models, then it is not necessary to lavish time and energy to apply them to more complex flow problems.


Assuntos
Hidrodinâmica , Modelos Moleculares , Polímeros/química , Cinética , Resistência ao Cisalhamento
3.
Proc Natl Acad Sci U S A ; 93(15): 7440-5, 1996 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-11607693

RESUMO

It is shown how the phase-space kinetic theory of polymeric liquid mixtures leads to a set of extended Maxwell-Stefan equations describing multicomponent diffusion. This expression reduces to standard results for dilute solutions and for undiluted polymers. The polymer molecules are modeled as flexible bead-spring structures. To obtain the Maxwell-Stefan equations, the usual expression for the hydrodynamic drag force on a bead, used in previous kinetic theories, must be replaced by a new expression that accounts explicitly for bead-bead interactions between different molecules.

4.
Gut ; 23(1): 80-2, 1982 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-7056501

RESUMO

A case of fatal cryptosporidiosis in a child with primary immunoglobulin deficiency is described. This is always a serious complication in immunodeficient patients because there is no known effective therapy.


Assuntos
Agamaglobulinemia/complicações , Coccidiose/complicações , Síndromes de Malabsorção/etiologia , Pré-Escolar , Doença Crônica , Coccidiose/patologia , Humanos , Jejuno/patologia , Masculino
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