Two-network theory

The two-network theory for a composite network of Gaussian chains was originally developed by Berry, Scanlan, and Watson (18) and then further developed by Flory ( 9). The composite network is made by introducing chemical cross-links in the isotropic and subsequently in a strained state. The Helmholtz elastic free energy of a composite network of Gaussian chains with affine motion of the junction points is given by the following expression ... 

Figure 2. The principle of the two-network method for cross-linking in a state of simple extension. First network with modulus Gy is entirely due to chain entangling. Second network with modulus Gx is formed by cross-linking in the strained state. Both Gy and Gx can be calculated from the two-network theory.

Neuronal networks are nowadays predominantly applied in classification tasks. Here, three kind of networks are tested First the backpropagation network is used, due to the fact that it is the most robust and common network. The other two networks which are considered within this study have special adapted architectures for classification tasks. The Learning Vector Quantization (LVQ) Network consists of a neuronal structure that represents the LVQ learning strategy. The Fuzzy Adaptive Resonance Theory (Fuzzy-ART) network is a sophisticated network with a very complex structure but a high performance on classification tasks. Overviews on this extensive subject are given in [2] and [6]. 

Allanic AL, Jezequel JY, Andre JC (1992) Application of neural networks theory to identify two-dimensional fluorescence spectra. Anal Chem 64 2618... 

The expressions given in this section, which are explained in more detail in Erman and Mark [34], are general expressions. In the next section, we introduce two network models that have been used in the elementary theories of elasticity to relate the microscopic deformation to the macroscopic deformation the affine and the phantom network models. 

The two-network method has been carefully examined. All the previous two-network results were obtained in simple extension for which the Gaussian composite network theory was found to be inadequate. Results obtained on composite networks of 1,2-polybutadiene for three different types of strain, namely equibiaxial extension, pure shear, and simple extension, are discussed in the present paper. The Gaussian composite network elastic free energy relation is found to be adequate in equibiaxial extension and possibly pure shear. Extrapolation to zero strain gives the same result for all three types of strain The contribution from chain entangling at elastic equilibrium is found to be approximately equal to the pseudo-equilibrium rubber plateau modulus and about three times larger than the contribution from chemical cross-links. 

A new stress-relaxation two-network method is used for a more direct measurement of the equilibrium elastic contribution of chain entangling in highly cross-linked 1,2-polybutadiene. The new method shows clearly, without the need of any theory, that the equilibrium contribution is equal to the non-equilibrium stress-relaxation modulus of the uncross-linked polymer immediately prior to cross-linking. The new method also directly confirms six of the eight assumptions required for the original two-network method. 

It is clearly shown that chain entangling plays a major role in networks of 1,2-polybutadiene produced by cross-linking of long linear chains. The two-network method should provide critical tests for new molecular theories of rubber elasticity which take chain entangling into account. 

Besides the two most well-known cases, the local bifurcations of the saddle-node and Hopf type, biochemical systems may show a variety of transitions between qualitatively different dynamic behavior [13, 17, 293, 294, 297 301]. Transitions between different regimes, induced by variation of kinetic parameters, are usually depicted in a bifurcation diagram. Within the chemical literature, a substantial number of articles seek to identify the possible bifurcation of a chemical system. Two prominent frameworks are Chemical Reaction Network Theory (CRNT), developed mainly by M. Feinberg [79, 80], and Stoichiometric Network Analysis (SNA), developed by B. L. Clarke [81 83]. An analysis of the (local) bifurcations of metabolic networks, as determinants of the dynamic behavior of metabolic states, constitutes the main topic of Section VIII. In addition to the scenarios discussed above, more complicated quasiperiodic or chaotic dynamics is sometimes reported for models of metabolic pathways [302 304]. However, apart from few special cases, the possible relevance of such complicated dynamics is, at best, unclear. Quite on the contrary, at least for central metabolism, we observe a striking absence of complicated dynamic phenomena. To what extent this might be an inherent feature of (bio)chemical systems, or brought about by evolutionary adaption, will be briefly discussed in Section IX. 

The challenge is therefore to develop an experiment which allows an experimental separation of the contributions from chain entangling and cross-links. The Two-Network method developed by Ferry and coworkers (17,18) is such a method. Cross-linking of a linear polymer in the strained state creates a composite network in which the original network from chain entangling and the network created by cross-linking in the strained state have different reference states. We have simplified the Two-Network method by using such conditions that no molecular theory is needed (1,21). 

In general, it appears that the fraction of configurations in the various topological classes can be determined for models in which one of the elements is a fixed curve and the other is a random coil. The detailed calculations are intricate and difficult, however, and some simple generalizations are needed which could be used as a step towards building classification effects into the network theories. Classification for the case of two random coils and for self-entanglement are unsolved problems at the present time. 

With these comments in mind, we list and briefly discuss the two classes of these theories the single molecule (14) and entanglement network theories (23). 

Two different constitutive equations, namely the Wagner model and the Phan Thien Tanner model, both based on network theories, have been investigated as far as their response to simple shear flow and uniaxial elongational flow is concerned. This work was primarily devoted to the determination of representative sets of parameters, that enable a correct description of the experimental data for three polyethylenes, to be used in numerical calculation in complex flows. Additionally, advantages and problems related to the use of these equations have been reviewed. 

The resistance distance is based on electrical network theory and is defined as the effective electrical resistance between two vertices (nodes) when a battery is connected across them and each graph edge is considered as a resistor taking a value of 1 ohm. 

It is extremely interesting that Eq. (4.23) is in fact identical with the constitutive equation obtained for Lodge s (48) network theory for the particular case of a network with a single time constant. The constants, of course, have a different interpretation. It is quite striking that two such very different structural theories should lead to the same macroscopic equations. 

---