Amorphous polymers experimental studies

Sihcate solutions of equivalent composition may exhibit different physical properties and chemical reactivities because of differences in the distributions of polymer sihcate species. This effect is keenly observed in commercial alkah sihcate solutions with compositions that he in the metastable region near the solubihty limit of amorphous sihca. Experimental studies have shown that the precipitation boundaries of sodium sihcate solutions expand as a function of time, depending on the concentration of metal salts (29,58). Apparently, the high viscosity of concentrated alkah sihcate solutions contributes to the slow approach to equihbrium. 

The toughness of interfaces between immiscible amorphous polymers without any coupling agent has been the subject of a number of recent studies [15-18]. The width of a polymer/polymer interface is known to be controlled by the Flory-Huggins interaction parameter x between the two polymers. The value of x between a random copolymer and a homopolymer can be adjusted by changing the copolymer composition, so the main experimental protocol has been to measure the interface toughness between a copolymer and a homopolymer as a function of copolymer composition. In addition, the interface width has been measured by neutron reflection. Four different experimental systems have been used, all containing styrene. Schnell et al. studied PS joined to random copolymers of styrene with bromostyrene and styrene with paramethyl styrene [17,18]. Benkoski et al. joined polystyrene to a random copolymer of styrene with vinyl pyridine (PS/PS-r-PVP) [16], whilst Brown joined PMMA to a random copolymer of styrene with methacrylate (PMMA/PS-r-PMMA) [15]. The results of the latter study are shown in Fig. 9. 

The character of the polymethyl methacrylate data is essentially similar to that found for systems atactic polystyrene-benzene at 25°, 35°, and 50° C. [Kishimoto, Fujita, Odani, Kurata and Tamura (1960) Odani, Kida, Kurata and Tamura (1961)] and also atactic polystyrene-methyl ethyl ketone at 25° C. [Odani, Hayashi and Tamura (1961)], and appears to be fairly general for amorphous polymer-solvent systems in the glassy state. On the other hand, the cellulose nitrate data shown in Fig. 8 appear to manifest features characteristic of crystalline polymer-solvent systems. For example, the earlier data of Newns (1956) on the system regenerated cellulose-water (in this case, water is not the solvent but merely a swelling-agent) and recent studies for several crystalline polymers all show essentially similar characters [see Kishimoto, Fujita, Odani, Kurata and Tamura (I960)]. To arrive at a more definite conclusion, however, more extensive experimental data are needed. 

The current interest is the examination of the consequences of fiee-volume theory on the effect of the solvent size on diffusional behavior, and the behavior of the diffusion process near the glass transition. Clearly, these two problems are interrelated. The experimental data needed to investigate both are accurate diffu-sivity-temperature data for a series of solvents that covers a wide range of molecular sizes. The series of solvents used should include solvents of large molecular size, incapable of segmental motion. Some recent work is reported hoe using polymethyl methacrylate, an amorphous polymer that can be studied over a wide temperature range. 

For our experimental studies on polymer crystallization we used low molecular weight (Mw) poly(ethylene oxide) (PEO), either as a homopolymer or attached to an amorphous polystyrene or hydrogenated polybutadiene block. These block copolymers are abbreviated by PS-PEO and PB, -PEO, respectively. PEO is a weU-investigated polymer [5,19,36,37]. Molecular details of all investigated polymers are given in Table 1. 

In Section 9.3 we present experimental studies of plastic deformation in two semi-crystalline polymers, HDPE and Nylon-6, both in tension and in plane-strain compression flow, from initial spherulitic morphologies to large plastic strains. In these studies, the evolving morphological alterations were monitored closely by a complementary array of techniques involving light microscopy and X-ray diffraction and scattering both in the crystalline and in the amorphous components. 

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