The Glass Transition Temperature, Tg

It is reasonable to assume that the glass transition temperature Tg drops linearly with increase in chain-end concentration, that is with an increase in the reciprocal of the molecular weight. This will give an equation of the form... 

If we, however, consider that viscosity is inversely related to the fractional free volume, which increases from a small value at the glass transition temperature Tg linearly with temperature above this figure, then it is possible to derive an equation. 

When the temperamre is lowered, rubbers become stiff and brittle. All rubbers eventually stiffen to a rigid, amorphous glass at the glass transition temperature (Tg). This temperature also indicates the low-temperature service limit of the rubber. Tg values are dependent on the structure, degree of cross-linking (vulcanization) and isomeric composition of the rubber. 

With plastics there is a certain temperature, called the glass transition temperature, Tg, below which the material behaves like glass i.e. it is hard and rigid. As can be seen from Table 1.8 the value for Tg for a particular plastic is not necessarily a low temperature. This immediately helps to explain some of the differences which we observe in plastics. For example, at room temperature polystyrene and acrylic are below their respective Tg values and hence we observe these materials in their glassy state. Note, however, that in contrast, at room temperature, polyethylene is above its glass transition temperature and so we observe a very flexible matoial. When cooled below its Tg it then becomes a hard, brittle solid. Plastics can have several transitions. 

Differential scanning calorimetry (DSC) is fast, sensitive, simple, and only needs a small amount of a sample, therefore it is widely used to analyze the system. For example, a polyester-based TPU, 892024TPU, made in our lab, was blended with a commercial PVC resin in different ratios. The glass transition temperature (Tg) values of these systems were determined by DSC and the results are shown in Table 1. 

There are three major measurements used in judging TPU as a polymeric plasticizer for PVC the glass transition temperature (Tg), the compatibility with PVC, and the degree of crystallinity. 

The glass transition temperatures (Tg) of both modified and unmodified PSs were determined by DSC analysis, and thermomechanic analysis was controlled by TMK. The results are given in Table 8. It is seen from Table 8 that the highest glass transition temperature (410 K) was obtained with chlorohydrinated PS and that of the lowest (370 K) with olefinic PS. The lowest glass transition temperature in the alkenylated PS caused to elasticity properties on polybutadien and polyisopren fragments. 

Figure 6. Composition dependence of the glass-transition temperature Tg for bulk amorphous Pd Cugo. xPzo-...

Orientation and mobility Orientation requires considerable mobility of large segments of the plastic molecules. It cannot occur below the glass transition temperature (Tg). The plastic temperature is taken just above Tg. 

The glass transition temperature Tg of the polymers remained constant and was not increased by extended heat treatment up to 240 °C. 

Molecular Motion in amorphous atactic polystyrene (PS) is more complicated and a number of relaxation processes, a through 5 have been detected by various techniques as reviewed recently by Sillescu74). Of course, motions above and below the glass transition temperature Tg have to be treated separately, as well as chain and side group mobility, respectively. Motion well above Tg as well as phenyl motion in the glassy state, involving rapid 180° jumps around their axes to the backbone has been discussed in detail in Ref.17). Here we will concentrate on chain mobility in the vicinity of the glass transition. 

Measurements of heat capacity jumps at the glass-transition temperatures, Tg, in the matrix material and the composites, carried out from heat-capacity experiments, were intimately related to the extent of the mesophase thickness. Further accurate measurements of the overall longitudinal elastic modulus of the composites and the... 

This difference in spatial characteristics has a profound effect upon the polymer s physical and chemical properties. In thermoplastic polymers, application of heat causes a change from a solid or glassy (amorphous) state to a flowable liquid. In thermosetting polymers, the change of state occurs from a rigid solid to a soft, rubbery composition. The glass transition temperature, Tg, ... 

Another example involved a batch of isocyanate crosslinker which was too tacky. Upon comparing the HPGPC trace of this sample with that of a control as shown in Figure 9, it is seen that the major difference between these two samples was the level of free caprolactam. The high content of free caprolactam in sample CX-006 depressed the glass transition temperature (Tg) of the sample to such an extent that CX-006 became too tacky. This method of analysis has proved to be a reliable and useful technique for detecting low levels of free caprolactam in this type of oligomeric crosslinker. 

Thermal Properties. The glass transition temperature (Tg) and the decomposition temperature (Td) were measured with a DuPont 910 Differential Scanning Calorimeter (DSC) calibrated with indium. The standard heating rate for all polymers was 10 °C/min. Thermogravimetric analysis (TGA) was performed on a DuPont 951 Thermogravimetric Analyzer at a heating rate of 20 °C/min. 

Both the glass-transition temperature (Tg) and the melting temperature (T of a polymer dictate whether the material is likely to be elastomeric at service... 

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