Intrinsic viscosities of cellulose acetates of degrees of substitution 2.86 and 3.00 and of cellulose trinitrate have been investigated as functions of temperature, solvent, and molecular weight. Large negative temperature coefficients (ca. −0.6% per degree) of [η] appear to be characteristic of cellulosic chains. These observed decreases in [η] with temperature are due to increases in chain flexibility, which are reflected in decreases in the characteristic ratio r 02/M. The rather large variations in [η] with the solvent are shown also to be manifestations of altered chain flexibilities brought about in some manner, as yet unexplained, by specific solvent interaction. This behavior stands in marked contrast to that of other polymers for which r 02/M is independent of the solvent and varies only slightly with temperature, and for which solvent effects on [η] are wholly attributable to changes in the molecular expansion (α3) brought about by solvent action,
Tensile stress‐induced crazing in polystyrene, poly(methyl methacrylate), and polycarbonate has been carefully examined by optical and electron microscopy. Examination of the surface of crazed specimens and the cross sections of individual crazes leads to the conclusion that the crazes are not void cracks, but are filled with a craze matter. The craze matter is readily distinguishable from the surrounding resin and is seen to exist in continuity with it. Further experiments confirm the existence of the craze matter and tend to indicate its structural and mechanical properties. These experiments include: microscopic examination of the walls of fractured crazes, micro x‐ray diffraction of craze matter, studies of the strength of crazed specimens under static loads and under increasing tensions, studies of the effect of heat and solvent on crazed specimens, and observations on the ability of crazes to form special networks. The results indicate that the craze matter may be formed by localized resin deformation leading to a load bearing oriented structure. A hypothesis of the mechanism of craze formation is proposed in light of the new and varied information reported in the paper. Study of the kinetics of craze growth suggests the division of the mechanism into three parts: initiation, propagation, and termination. The initiation step describes the concentration of strain energy and the precursory molecular arrangements in the immediate vicinity of inhomogeneities. These are the changes which occur during the time lapse between stress application and first appearance of crazes. The propagation step comprises the sudden and relatively rapid localized resin deformation which creates the craze matter. The shapes of the growing crazes and their diminishing growth rates are attributable to known resin properties. The termination step represents the apparent cessation of craze growth with continued long times of stress application. At this stage in the existence of crazes the proposed hypothesis must blend into the theories of time delayed rupture. It is concluded that stress crazing is basically a molecular slippage rather than a molecular cleavage phenomenon. Considerations, therefore, are to be directed more towards intermolecular forces than intramolecular forces.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.