Continuous semicrystalline

When we begin to stretch a semicrystalline polymer it deforms affinely, that is, each element of the sample within the gauge region experiences identical stress and strain. As we continue to stretch the sample, we reach a point at which affine deformation ceases and the sample yields. At this point, it typically develops a local region of reduced cross-sectional area, known... 

PTT polymer pellets must be dried to a moisture level of <30 ppm, preferably in a close-loop hot air dryer, to avoid hydrolytic degradation during melt processing. Drying is carried out with 130 °C hot air with a dew point of < -40 °C for at least 4 h. Because of the faster crystallization rate, PTT pellets are already semicrystalline after pelletizing, and do not require pre-crystallization prior to drying as with PET. The dried polymer is extruded at 250-270 °C into bulk continuous filaments (BCFs), partially oriented yam (POY), spin-draw yam (SDY) and staple fiber. 

In semicrystalline polymers such as polyethylene, yielding involves significant disruption of the crystal structure. Slip occurs between the crystal lamellae, which slide by each other, and within the individual lamellae by a process comparable to glide in metallic crystals. The slip within the individual lamellae is the dominant process, and leads to molecular orientation, since the slip direction within the crystal is along the axis of the polymer molecule. As plastic flow continues, the slip direction rotates toward the tensile axis. Ultimately, the slip direction (molecular axis) coincides with the tensile axis, and the polymer is then oriented and resists further flow. The two slip processes continue to occur during plastic flow, but the lamellae and spherullites increasingly lose their identity and a new fibrillar structure is formed (see Figure 5.69). 

PE crystal, the penetration length of the mechanical excitation into the lamella was found to be about 5 nm. As a result, if the tie molecule ends in the lamella or continues and ends in an amorphous region, the axial forces it can be exposed to are very small. Such a tie molecule contributes very little to the strength of a semicrystalline solid. 

Through the use of multiple experimental techniques, we have shown how both the NXL and XL phases of PILE interact and respond to applied tensile deformation. Strains transmitted to PILE crystals lead to two distinct slip modes and, at higher strains, to the breakup and alignment of lamellar fragments. In our experiments, crystallites in PTFE orient fuUy with respect to the draw direction at strains between 70 to 200%. With increasing strain, some chains originally in the XL phase are transformed to NXL material. Noncrystalline chains continue to orient until macroscopic failure is reached. This could be a fairly general microstructural response for semicrystalline polymers. 

PE-PEP diblock were similar to each other at high PE content (50-90%). This was because the mechanical properties were determined predominantly by the behaviour of the more continuous PE phase. For lower PE contents (7-29%) there were major differences in the mechanical properties of polymers with different architectures, all of which formed a cubic-packed sphere phase. PE-PEP-PE triblocks were found to be thermoplastic elastomers, whereas PEP-PE-PEP triblocks behaved like particulate filled rubber.The difference was proposed to result from bridging of PE domains across spheres in PE-PEP-PE triblocks, which acted as physical cross-links due to anchorage of the PE blocks in the semicrystalline domains. No such arrangement is possible for the PEP-PE-PEP or PE-PEP copolymers (Mohajer et al. 1982). 

Table 4.3 shows the permselectivity characteristics of pure, semicrystalline PEO films [76]. The selectivity characteristics for 02/N2 are rather similar to those for silicone rubber and natural rubber shown in Table 4.2. However, the values of permselectivity for C02 relative to the various light gases shown are all much higher than Table 4.2 shows for the rubbery polymers listed there and even for polysulfone except for C02/CH4. Comparison of the data in Tables 4.2 and 4.3 makes it clear that this high permselectivity of PEO stems from its high solubility selectivity for C02 versus other gases this is augmented by modest values of diffusivity selectivity. Data in Table 4.4 for the C02/N2 pair illustrate that this effect can be translated into various block-copolymer structures when the PEO content is high enough to ensure it is the continuous phase. In fact, nearly all these materials have higher permselectivity and solubility selectivity for C02/N2 than does pure PEO (see Table 4.3) however, the diffusion selectivity for these copolymers is much closer to, or even less than, unity than seen for pure PEO. Furthermore, the copolymers all have much higher absolute permeability coefficients than does PEO.

After the additions have been completed, the third neck of the flask is closed and the temperature of the stirred reaction mixture is raised to its boiling point during 15-20 minutes, then heating under reflux is continued for 10-15 minutes. The contents of the flask, which first change to a greenish yellow dear solution, then later separate into two phases, are kept well mixed by rapid stirring (Note 2). The flask is next disconnected, fitted with a stillhead, and the acetone is distilled rapidly at 25-35° under reduced pressure. The residual semicrystalline suspension, or two-phase mixture containing the crude product in the upper viscous layer, is carefully stirred onto 300-400 g. of crushed ice. 

Starch is a semicrystalline polymer. The linear amylose molecules are amorphous in nature, but the branched amylopectin portion has been reported as partially crystalline. It is believed that the crystalline regions in the starch granule are interspersed in a continuous amorphous phase. ° ... 

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