Amorphous dynamic mechanical measurement

Dynamic mechanical measurements were made on PTEE samples saturated with various halocarbons (88). The peaks in loss modulus associated with the amorphous relaxation near —90°C and the crystalline relaxation near room temperature were not affected by these additives. An additional loss peak appeared near —30° C, and the modulus was reduced at all higher temperatures. The amorphous relaxation that appears as a peak in the loss compliance at 134°C is shifted to 45—70°C in the swollen samples. 

Transitions. Samples containing 50 mol % tetrafluoroethylene with ca 92% alternation were quenched in ice water or cooled slowly from the melt to minimise or maximize crystallinity, respectively (19). Internal motions were studied by dynamic mechanical and dielectric measurements, and by nuclear magnetic resonance. The dynamic mechanical behavior showed that the CC relaxation occurs at 110°C in the quenched sample in the slowly cooled sample it is shifted to 135°C. The P relaxation appears near —25°C. The y relaxation at — 120°C in the quenched sample is reduced in peak height in the slowly cooled sample and shifted to a slightly higher temperature. The CC and y relaxations reflect motions in the amorphous regions, whereas the P relaxation occurs in the crystalline regions. The y relaxation at — 120°C in dynamic mechanical measurements at 1 H2 appears at —35°C in dielectric measurements at 10 H2. The temperature of the CC relaxation varies from 145°C at 100 H2 to 170°C at 10 H2. In the mechanical measurement, it is 110°C. There is no evidence for relaxation in the dielectric data. 

The measurements of Young s modulus in dependence of the temperature (dynamic-mechanical measurements, see Sect. 2.3.5.2) and the differential thermal analysis (DTA or DSC) are the most frequently used methods for determination of the glass transition temperature. In Table 2.10 are listed and values for several amorphous and crystalline polymers. 

In another paper in this issue [1], the molecular motions involved in secondary transitions of many amorphous polymers of quite different chemical structures have been analysed in detail by using a large set of experimental techniques (dynamic mechanical measurements, dielectric relaxation, H, 2H and 13C solid state NMR), as well as atomistic modelling. 

The NMR data presented above reveal a dynamic heterogeneity of filled PDMS in the frequency range from about 10 kHz to 100 MHz. To determine whether the heterogeneity remains at lower fi equencies, dynamic mechanical measurements are performed. The results for cured, unfilled silicon rubber are compared with those for filled samples containing different fraction of hydrophilic Aerosil (380 m g ). For a more straightforward analysis of the mechanical experiments, a random poly(dimethyl/methyl-phenyl) siloxane copolymer containing approximately 90 mol% dimethyl- and 10 mol% methylphenyl-siloxane units has been used for sample preparation. This copolymer is fully amorphous over the whole temperature range. The results of torsion experiments at a frequency of 1.6 Hz are shown as a function of temperature in Fig. 7. 

Dynamic mechanical measurements (DMA) provide information that is complementary to the creep and stress relaxation experiments. Frosini and Butta studied amorphous wholly aromatic polyamides and found for PpPTA small relaxation peaks at about 15 °C, 145 °C and above 330 °C [195]. Except for the peak at 15 °C, the peak heights are much smaller than those measured for aUphatic and partially aromatic polyamides. The peak at 15 °C is identified as a -relaxation and probably caused by the motions of free amide groups. The a-relaxation or... 

Cellulose nitrate In diethyl phthalate (23%) Polyethylene (solution chlorinated) Cl content = 56.6 w/w, amorphous, in bis(2-ethylhexyl)phthalate 298 8.84 165.5 166 ar,s from creep and dynamic mechanical measurements. 

Generally, it is possible to obtain data from broad-band NMR spectroscopy that compares favorably with dynamic-mechanical measurements of polymers. The two types of data, NMR and dynamic-mechanical, complement each other in that, for some physical or chemical changes that occur in the polymer, both methods check each other or, alternatively, one method gives results which the other method cannot give. For example, both amorphous and crystalline phase changes can be detected by NMR and dynamic-mechanical measurements. Some crystalline melt transitions cannot be detected by NMR. In addition some secondary amorphous transitions in polymers cannot be detected by NMR. On the other hand, NMR is a more sensitive technique for determining side chain ro-... 

The X-ray diffraction (XRD) profiles of the TPUs show an amorphous shoulder at about 29 = 20° (Figure 17) and a very sharp glass-rubber transition at about 60°C is obtained from dynamic mechanical measurements (Figure 18). It is seen... 

Luck, W.A.P. 1981. Structures of water in aqueous systems. In Water Activity Influences on Food Quality (L.B. Rockland and G.F. Stewart, eds), pp. 407 134. Academic Press, New York. Ludescher, R.D., Shah, N.K., McCaul, C.P., and Simon, K.V. 2001. Beyond Tg Optical luminescence measurements of molecular mobility in amorphous solid foods. Food Hydro colloids 15, 331-339. Ludwig, R. 2001. Water From cluster to the bulk. Angewandte Chem. Int. Ed. 40, 1808-1827. Maclnnes, W.M. 1993. Dynamic mechanical thermal analysis of sucrose solutions. In The Glassy State in Foods (J.M.V. Blanshard and PJ. Lillford, eds), pp. 223-248. Nottingham Univ. Press, Loughborough, Leicestershire. 

DSC measurements showed that the crystallization ability of this interphase region was reduced by the silane modification of the glass beads. Despite an increase in the amount of amorphous material with increasing number of silane layers, a decrease in the intensity of the fourth lifetime was observed. This decrease in the free volume is in accordance with the earlier observed reduced mobility in the interphase region measured by dynamic-mechanical spectroscopy in the melt state [9,10] and creep and stress relaxation measurements in the solid state [12]. 

Enthalpy relaxation time, determined by differential scanning calorimetry,608 and mechanical relaxation, determined by dynamic mechanical analysis,609 can also be used as measures of molecular mobility of amorphous pharmaceutical solids. 

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