Glass transition temperature model

We present here a simple experiment, conceived to test both the reptation model and the minor chain model, by Welp et al. [50] and Agrawal et al. [51-53]. Consider the HDH/DHD interface formed with two layers of polystyrene with chain architectures shown in Fig. 5. In one of the layers, the central 50% of the chain is deuterated. This constitutes a triblock copolymer of labeled and normal polystyrene, which is, denoted HDH. In the second layer, the labeling has been reversed so that the two end fractions of the chain are deuterated, denoted by DHD. At temperatures above the glass transition temperature of the polystyrene ( 100°C), the polymer chains begin to interdiffuse across the... 

Hamiltonian does not give rise to any crystalline order in the system. By employing models hke this, the quench-rate and chain-length dependence of the glass transition temperature, as well as time-temperature superposition, similar to experiments [23], were investigated in detail. 

In this approach, connectivity indices were used as the principle descriptor of the topology of the repeat unit of a polymer. The connectivity indices of various polymers were first correlated directly with the experimental data for six different physical properties. The six properties were Van der Waals volume (Vw), molar volume (V), heat capacity (Cp), solubility parameter (5), glass transition temperature Tfj, and cohesive energies ( coh) for the 45 different polymers. Available data were used to establish the dependence of these properties on the topological indices. All the experimental data for these properties were trained simultaneously in the proposed neural network model in order to develop an overall cause-effect relationship for all six properties. 

Figure 25 ANN model (5-8-6) training and testing results for van der Waals volume, molar volume, heat capacity, solubility parameter, and glass transition temperature of 45 different polymers.

Naqvi [134] has proposed an alternative model to the Frye and Horst mechanism for the degradation and stabilization of PVC. At room temperature, PVC is well below its glass transition temperature (about 81°C). The low thermal stability of the polymer may be due to the presence of undesirable concentrations of like-poles in the more or less frozen matrix with strong dipoles. Such concentrations, randomly distributed in the polymer matrix, may be considered to constitute weak or high energy spots in the polymer, the possible sites of initiation of thermal dehydrochlorination. 

In order to simplify the procedure of evaluating the extent of mesophase and its mechanical and thermal properties, a simple but effective three-layer model may be used, which is based on measurements of the thermal expansions of the phases and the composite, below and above the transition zone of the composite, lying around its glass transition temperature Tgc. 

Indeed, the multi-layered model, applied to fiber reinforced composites, presented a basic inconsistency, as it appeared in previous publications17). This was its incompatibility with the assumption that the boundary layer, constituting the mesophase between inclusions and matrix, should extent to a thickness well defined by thermodynamic measurements, yielding jumps in the heat capacity values at the glass-transition temperature region of the composites. By leaving this layer in the first models to extent freely and tend, in an asymptotic manner, to its limiting value of Em, it was allowed to the mesophase layer to extend several times further, than the peel anticipated from thermodynamic measurements, fact which does not happen in its new versions. 

As a consequence, the overall penetrant uptake cannot be used to get direct informations on the degree of plasticization, due to the multiplicity of the polymer-diluent interactions. The same amount of sorbed water may differently depress the glass transition temperature of systems having different thermal expansion coefficients, hydrogen bond capacity or characterized by a nodular structure that can be easily crazed in presence of sorbed water. The sorption modes, the models used to describe them and the mechanisms of plasticization are presented in the following discussion. 

A simple algorithm [17] makes it possible to find the probability of any fragment of macromolecules of Gordonian polymers. Comparison of these probabilities with the data obtained by NMR spectroscopy provides the possibility to evaluate the adequacy of a chosen kinetic model of a synthesis process of a particular polymer specimen. The above-mentioned probabilities are also involved in the expressions for the glass transition temperature and some structure-additive properties of branched polymers [18,19]. 

From the dynamic mechanical spectroscopy, an increase of PTMO molecular weight from 650 to 2000 results in a decrease in both the modulus and the glass transition temperature of the final product. The SAXS results indicate that a correlation distance exists in the samples, and this distance increases as PTMO molecular weight increases. A cluster model is thus suggested to account for the experimental results. 

Indeed, it has been observed that the onset of yielding of isotropic polymers is approximately constant, 0.02< [<0.025, which implies that 0.04shear yield strain, the plastic shear deformation of the domain satisfies a plastic shear law. For temperatures below the glass transition temperature, the continuous chain model enables the calculation of the tensile curve of a polymer fibre up to about 10% strain [6]. Figure 7 shows the observed stress-strain curves of PpPTA fibres with different moduli compared to the calculated curves. 

In view of the development of the continuous chain model for the tensile deformation of polymer fibres, we consider the assumptions on which the Coleman model is based as too simple. For example, we have shown that the resolved shear stress governs the tensile deformation of the fibre, and that the initial orientation distribution of the chains is the most important structural characteristic determining the tensile extension below the glass transition temperature. These elements have to be incorporated in a new model. 

Peleg, M. 1996. On modeling changes in food and biosolids at and around their glass transition temperature range. Crit. Rev. Food Sci. Nutr. 36, 49-67. 

Glass transition temperatures of the uv-hardened films were measured with a Perkin Elmer Model DSC-4 differential scanning calorimeter (DSC) that was calibrated with an indium standard. The films were scraped from silicon substrates and placed in DSC sample pans. Temperature scans were run from -40 to 100-200 °C at a rate of 20 ° C/min and the temperature at the midpoint of the transition was assigned to Tg. 

We now turn to a characterization of the dynamics in a polymer melt where, as it is supercooled, it approaches its glass transition temperature. We begin by looking at the translational dynamics in a bead-spring model and consider its analysis in terms of MCT. 

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