ABSTRACT:The effect of fiber orientation on the toughening of polymers by short glass fibers generally below their critical length was investigated using specimens with either well-aligned or randomly oriented fibers. The fibers were aligned by an electric field in a photopolymerizable monomer, which was polymerized while the field was still being applied. These materials were fractured with the aligned fibers in three orientations with respect to the crack plane and propagation direction. Specimens with fibers aligned normal to the fracture plane were the most tough, those with randomly oriented fibers were less tough, and those with fibers aligned within the fracture plane were the least tough. The fracture behaviors compared favorably with predictions based on observed processes accounting for fiber orientation. The processes considered were fiber pull-out (including snubbing), fiber breakage, fiber-matrix debonding, and localized matrix-yielding adjacent to fibers bridging the fracture plane. Fibers not quite perpendicular to the fracture plane provided the greatest toughening; these fibers pulled out completely and gave a significant contribution from snubbing. Fibers at higher angles provided less toughening, involving nearly equal contributions from pull-out, breakage, and debonding. Fibers within the fracture plane provided the least toughening, involving debonding alone.
While theoretical and experimental efforts have thoroughly addressed microphase‐ordered AB diblock copolymer blends with a parent homopolymer (hA or hB) or a second block copolymer, surprisingly few studies have considered comparable ABA triblock copolymers in the presence of hB or an AB diblock copolymer. In this study, we elucidate the roles of additive molecular weight and constraint by examining three matched series of miscible ABA/hB and ABA/AB blends. Self‐consistent field theory is employed to analyze molecular characteristics, e. g., segmental distributions, microdomain periods and midblock bridging fractions, as functions of blend composition. Predictions are compared to morphological characteristics discerned by transmission electron microscopy and small‐angle X‐ray scattering. The corresponding mechanical properties of these blends are measured by dynamic mechanical analysis. The results of this comprehensive work reveal that addition of hB swells the B‐lamellae of the ABA copolymer and has a generally deleterious effect on both the dynamic elastic modulus and midblock bridging fraction. In contrast, addition of a lamellar or cylindrical AB copolymer to the same ABA copolymer can promote an increase or decrease in lamellar period and bridging fraction, depending on relative block sizes.
Recent studies have demonstrated that addition of a small quantity of dibenzylidene sorbitol (DBS) to a molten polymer may result in a physical gel if conditions permit the DBS molecules to self-organize into a three-dimensional network composed of highly connected nanofibrils. If the polymer crystallizes, DBS may also serve as a nucleating agent, promoting the formation of spherulites, especially in commercially important polyolefins such as polypropylene. We examine the thermal and mechanical properties, as well as the morphological characteristics, of an isotactic polypropylene copolymer with 3 wt % ethylene upon addition of less than 1 wt % of 1,3:2,4-di-pmethylbenzylidene sorbitol (MDBS). From dynamic rheological measurements, pronounced complex viscosity increases, attributed to MDBS nanofibril network formation, are observed at concentration-dependent temperatures above the melting point of the nucleated copolymer. Transmission electron micrographs of RuO 4 -stained sections confirm the existence of MDBS nanofibrils measuring on the order of 10 nm in diameter and, at higher concentrations, fibrillar bundles measuring up to about 200 nm across and several microns in length. The addition of MDBS at different concentrations is also found to promote increases in optical clarity, yield strength, tensile strength, and ultimate elongation of modified copolymer formulations.
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