Dynamic mechanical behavior method

Electron microscopy (5,40,52,63, 64), on the other hand, can provide direct information on the domain structure under favorable conditions, such as when the domains are crystalline. When the samples exhibit a semicrystalline superstructure, small-angle light scattering and polarized microscopy have been used in addition to electron microscopy to study the spherulitic structure. These methods are complemented by differential scanning calorimetry, and various techniques for studying dynamic mechanical behavior which can be interpreted to give additional, if somewhat less direct, information on domain structure. 

Johari, G. Mikoljaczak, G. Cavaille, J. Dynamic Mechanical behavior and its dependence on preparation method in structural epoxide resins. Polymer 1987, 28, 2023. 

Relaxations of a-PVDF have been investigated by various methods including dielectric, dynamic mechanical, nmr, dilatometric, and piezoelectric and reviewed (3). Significant relaxation ranges are seen in the loss-modulus curve of the dynamic mechanical spectmm for a-PVDF at about 100°C (a ), 50°C (a ), —38° C (P), and —70° C (y). PVDF relaxation temperatures are rather complex because the behavior of PVDF varies with thermal or mechanical history and with the testing methodology (131). 

There are several other comparable rheological experimental methods involving linear viscoelastic behavior. Among them are creep tests (constant stress), dynamic mechanical fatigue tests (forced periodic oscillation), and torsion pendulum tests (free oscillation). Viscoelastic data obtained from any of these techniques must be consistent data from the others. 

As predicted by Otis, the method is believed capable of detecting asynchronous mechanical behavior (unequal regional ventilatory time constants), which otherwise can be documented only by the considerably more difficult measurement of dynamic lung compliance. 

Dynamic mechanical analysis (DMA) or dynamic mechanical thermal analysis (DMTA) provides a method for determining elastic and loss moduli of polymers as a function of temperature, frequency or time, or both [1-13]. Viscoelasticity describes the time-dependent mechanical properties of polymers, which in limiting cases can behave as either elastic solids or viscous liquids (Fig. 23.2). Knowledge of the viscoelastic behavior of polymers and its relation to molecular structure is essential in the understanding of both processing and end-use properties. 

The dynamic mechanical thermal analyzer (DMTA) is an important tool for studying the structure-property relationships in polymer nanocomposites. DMTA essentially probes the relaxations in polymers, thereby providing a method to understand the mechanical behavior and the molecular structure of these materials under various conditions of stress and temperature. The dynamics of polymer chain relaxation or molecular mobility of polymer main chains and side chains is one of the factors that determine the viscoelastic properties of polymeric macromolecules. The temperature dependence of molecular mobility is characterized by different transitions in which a certain mode of chain motion occurs. A reduction of the tan 8 peak height, a shift of the peak position to higher temperatures, an extra hump or peak in the tan 8 curve above the glass transition temperature (Tg), and a relatively high value of the storage modulus often are reported in support of the dispersion process of the layered silicate. 

Dynamic mechanical experiments, where the material is periodically strained, are common methods to characterize the visco-elastic behavior of elastomers by measuring the storage modulus G and loss modulus G". G is a measure for the maximal, reversibly stored energy for a periodical deformation and G" is proportional to the dissipated energy for the oscillation cycle. It is obvious to investigate, whether the l.c. state of the l.c. elastomers influences the dynamic mechanical properties and whether different modes of linking the mesogenic moieties to the backbone can be detected. 

In this section we are going to examine such viscoelastic properties in some detail and we will start by examining in turn three important mechanical methods of measurement creep, stress relaxation, and dynamic mechanical analysis. This will lead us to interesting things like time-temperature equivalence and a discussion of the molecular basis of what we have referred to as relaxation behavior. 

Spectral analysis techniques to study the behavior of pol3rmers subjected to dynamic mechanical loads and/or deformation is called Fourier Transform Mechanical Analysis (FTMA). FTMA measures the complex moduli over a range of frequencies in one test by exciting the sample by a random signal (band limited white noise) (13.14). FTMA overcomes or circumvents problems inherent in other test methods because it measures dynamic mechanical properties over a wide range of frequency with minimal temperature and moisture changes within the sample. 

Another possibility of determining the gel point with the help of rheological methods is dynamical mechanical spectroscopy. Analysis of change of dynamic mechanical properties of reactive systems shows that the gel point time may be reached when tan S or loss modulus G" pass a miximum [3,4,13], Some authors proposed to correlate the gel point with the intersection point of the curves of storage and loss moduli, i.e., with the moment at which tan 5 = 1 [14-16], However, theoretical calculations have shown that the intersection point of storage modulus and loss modulus meets the gelation conditions only for a certain law of relaxation behavior of the material and the coincidence erf the moment of equality G = G" with the gel point is a particular case [17]. The variation of the viscosity... 

We have used X-ray methods to compare the crystallite size of RIM specimens prepared with and without use of a polyether diamine (PEDA) additive. These results are compared with differential scanning calorimetry data on the hard domain melting behavior and dynamic-mechanical studies of the extent of phase separation. Mechanical data on flexural modulus, elongation, impact strength, and heat sag behavior have been obtained for the same specimens and have been correlated with the structural analyses. 

---