Macroscopic behavior

Note that no assumptions involve fiber-reinforced composite materials explicitly. Instead, only the restriction to orthotropic materials at various orientations is significant because we treat the macroscopic behavior of an individual orthotropic (easily extended to anisotropic) lamina. Therefore, what follows is essentially a classical plate theory for laminated materials. Actually, interlaminar stresses cannot be entirely disregarded in laminated plates, but this refinement will not be treated in this book other than what was studied in Section 4.6. Transverse shear effects away from the edges will be addressed briefly in Section 6.6. 

It is the interplay of universal and material-specific properties which causes the interesting macroscopic behavior of macromolecular materials. This introduction will not consider scales beyond the universal or scaling regime, such as finite element methods. First we will give a short discussion on which method can be used under which circumstances. Then a short account on microscopic methods will follow. The fourth section will contain some typical coarse-grained or mesoscopic simulations, followed by some short general conclusions. 

Lattice gases are micro-level rule-based simulations of macro-level fluid behavior. Lattice-gas models provide a powerful new tool in modeling real fluid behavior ([doolenQO], [doolenQl]). The idea is to reproduce the desired macroscopic behavior of a fluid by modeling the underlying microscopic dynamics. 

While there are mairy variants of the basic, model, one can show that there is a well-defined minimal set of niles that define a lattice-gas system whose macroscopic behavior reproduces that predicted by the Navier-Stokes equations exactly. In other words, there is critical threshold of rule size and type that must be met before the continuum fluid l)cliavior is matched, and onec that threshold is reached the efficacy of the rule-set is no loner appreciably altered by additional rules respecting the required conservation laws and symmetries. 

Chapter 9 provides an introductory discussion of a research area that is rapidly growing in importance lattice gases. Lattice gases, which are discretized models of continuous fluids, represent an early success of CA modeling techniques. The chapter begins with a short primer on continuum fluid dynamics and proceeds with a discussion of CA lattice gas models. One of the most important results is the observation that, under certain constraints, the macroscopic behavior of CA models exactly reproduces that predicted by the Navier-Stokes equations. 

There are two levels, discrete particle level and continuum level, for describing and modeling of the macroscopic behaviors of dilute and condensed matters. The physics laws concerning the conservation of mass, momentum, and energy in motion, are common to both levels. For simple dilute gases, the Boltzmann equation, as shown below, provides the governing equation of gas dynamics on the discrete particle level... 

Ziabicki, A, Topological Structure and Macroscopic Behavior of Permanently Crosslinked Polymer Systems, Polymer 20, 1373, 1979. 

Hence, close to the critical point thermodynamic quantities at comparatively distant spatial locations become correlated. Especially in the case of liquid micro flows close to a phase transition, these considerations suggest that the correlation length and not the molecular diameter is the length scale determining the onset of deviations from macroscopic behavior. 

The principle of a lattice gas is to reproduce macroscopic behavior by modeling the underlying microscopic dynamics. In order to successfully predict the macro-level behavior of a fluid from micro-level rules, three requirements must be satisfied. First, the number of particles must be conserved and, in most cases, so is the particle momentum. States of all the cells in the neighborhood depend on the states of all the others, but neighborhoods do not overlap. This makes application of conservation laws simple because if they apply to one neighborhood they apply to the whole lattice. 

The subject of plastic deformation has suffered from attempts to interpret macroscopic behavior without adequate microscopic (and nanoscopic) information. This will always be the case to some extent, but it needs to be minimized. Also, since the size scale of dislocations is atomic, Heisenberg s principle and its implications must be considered in order to understand plastic deformation and, therefore, hardness. 

DPMs offer a viable tool to study the macroscopic behavior of assemblies of particles and originate from MD methods. Initiated in the 1950s by Alder and Wainwright (1957), MD is by now a well-developed method with thousands of papers published in the open literature on just the technical and numerical aspects. A thorough discussion of MD techniques can be found in the book by Allen and Tildesley (1990), where the details of both numerical algorithms and computational tricks are presented. Also, Frenkel and Smit (1996) provide a comprehensive introduction to the recipes of classical MD with emphasis on the physics underlying these methods. Nearly all techniques developed for MD can be directly applied to discrete particles models, except the formulation of particle-particle interactions. Based on the mechanism of particle-particle interaction, a granular system may be modeled either as hard-spheres or as soft-spheres. ... 

I of reaction as a reaction path). The important consequence is that the maximum / number of steps in a kinetics scheme is the same as the number (R) of chemical equations (the number of steps in a kinetics mechanism is usually greater), and hence stoichiometry tells us the maximum number of independent rate laws that we must obtain experimentally (one for each step in the scheme) to describe completely the macroscopic behavior of the system. 

In Fig. 1, various elements involved with the development of detailed chemical kinetic mechanisms are illustrated. Generally, the objective of this effort is to predict macroscopic phenomena, e.g., species concentration profiles and heat release in a chemical reactor, from the knowledge of fundamental chemical and physical parameters, together with a mathematical model of the process. Some of the fundamental chemical parameters of interest are the thermochemistry of species, i.e., standard state heats of formation (A//f(To)), and absolute entropies (S(Tq)), and temperature-dependent specific heats (Cp(7)), and the rate parameter constants A, n, and E, for the associated elementary reactions (see Eq. (1)). As noted above, evaluated compilations exist for the determination of these parameters. Fundamental physical parameters of interest may be the Lennard-Jones parameters (e/ic, c), dipole moments (fi), polarizabilities (a), and rotational relaxation numbers (z ,) that are necessary for the calculation of transport parameters such as the viscosity (fx) and the thermal conductivity (k) of the mixture and species diffusion coefficients (Dij). These data, together with their associated uncertainties, are then used in modeling the macroscopic behavior of the chemically reacting system. The model is then subjected to sensitivity analysis to identify its elements that are most important in influencing predictions. 

So far, we have seen that deviation from ideal behavior may affect one or more thermodynamic magnitudes (e.g., enthalpy, entropy, volume). In some cases, we are able to associate macroscopic interactions with real (microscopic) interactions of the various ions in the mixture (for instance, coulombic and repulsive interactions in the quasi-chemical approximation). In practice, it may happen that none of the models discussed above is able to explain, with reasonable approximation, the macroscopic behavior of mixtures, as experimentally observed. In such cases (or whenever the numeric value of the energy term for a given substance is more important than actual comprehension of the mixing process), we adopt general (and more flexible) equations for the excess functions. 

Polymers are real and all around us. We can look at giant molecules on a micro or atomic level or on a macroscopic level. The PET bottles we have may be composed of long chains of poly(ethylene terephthate) (PET) chains. The aramid tire cord is composed of aromatic polyamide chains. Our hair is made up of complex bundles of fibrous proteins, again polyamides. The polymers you study are related to the real world in which we live. We experience these large molecules at the macroscopic level everyday of our lives and this macroscopic behavior is a direct consequence of the atomic-level structure and behavior. Make pictures in your mind that allow you to relate to the atomic and macroscopic worlds. 

Phase behavior of lipid mixtures is a much more difficult problem, due to nonideal mixing of lipid components. Ideal mixing implies like and unlike lipids have the same intermolecular interactions, while nonideal mixing results from differential interactions between lipid types. If the difference is too great, the two components will phase separate. While phase separation and lateral domain formation have been observed in many experiments, we lack a molecular-level physical description of the interactions between specific lipids that cause the macroscopic behavior. The chemical potential of a lipid determines phase separation, as phase coexistence implies the chemical potential of each type of lipid is equal in all phases of the system [3,4],... 

This relation provides a simple closure to the iGLE in which the microscopic dynamics is connected to the macroscopic behavior. Because of this closure, the microscopic dynamics are said to depend self-consistently on the macroscopic (averaged) trajectory. Formally, this construction is well-defined in the sense that if the true (R(t)) is known a priori, then the system of equations return to that of the iGLE with a known g(t). In practice, the simulations are performed either by iteration of (R(t)) in which a new trajectory is calculated at each step and (R(t)) is revised for the next step, propagation of a large number of trajectories with (R(t)) calculated on-the-fly, or some combination thereof. 

Numerical simulations illustrating the role of diffusion in the onset of instabilities have been carried out by Hannusse.5 They confirm the modification of macroscopic behavior by local fluctuations that introduce such phenomena as delays or metastable states. 

Our objectives in this chapter are to look into the origin of van der Waals forces, see how they affect macroscopic behavior and properties of materials, and establish relations for scaling up the molecular-level forces to forces between macroscopic bodies. 

Two illustrations of the implications of these forces to macroscopic behavior of materials are also provided here. 

The computations described briefly in this paper illustrate the interrelationship between the local structure and macroscopic behavior of the DNA helix. Statistical mechanical studies help to identify the most likely morphological arrangements of the polynucleotide backbone and to understand the macroscopic flexibility of the DNA as a whole. Model building and potential energy calculations uncover the detailed local geometries of the chain and clarify the likely pathways between the multitude of allowed spatial forms. 

These glasses differ macroscopically in volume and, therefore, in structure. This mental experiment intends to point out, that correctly speaking, there does not exist a glass of definite structure. A glass of the composition x at the temperature T can be produced in different ways which result in glasses of different structure. The characteristic behavior of the plasticizer in its molecular interaction with the chain molecules determines structure and macroscopic behavior of the glass. 

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