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The deformation behavior of poly(styrene-b-butyl methacrylate) diblock copolymers, PS-b-PBMA, is studied by high-voltage electron microscopy (HVEM) with in-situ deformation device and by TEM. This allows us to describe the craze growth and propagation in block copolymers with different morphologies. The influence of shape and orientation of morphology on deformation mechanism is discussed in correlation with tensile properties. For lamellar, hexagonal, and lamellar/hexagonal structures diversion of crazes and craze stopping mechanisms are observed. The discussion of the dependence of craze initiation stress, σc, on morphology is used to correlate the micromechanical deformation processes with tensile properties. In contrast to other block copolymers, it is shown that σc exceeds the value of pure PS at 76% PS due to the hexagonal morphology, high miscibility, and broadened interface of PS-b-PBMA which explains the improved tensile properties of weakly segregated block copolymers. It is shown that microphase separated morphologies, phase behavior, and interface formation have a pronounced influence on deformation behavior of PS-b-PBMA diblock copolymers.

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Poly(styrene-b-butyl methacrylate) diblock copolymers, PS-b-PBMA, with different morphologies are investigated with respect to the influence of strain rate and temperature on tensile properties. In the first part the mechanical properties of bicontinuous and perforated lamellar structure are compared with other morphologies. Diblock copolymers with bicontinuous structures (39% PS) show a much higher tensile strength as well as a higher strain at break than diblock copolymers with lamellar structures (50% PS). In the second part the dependence of tensile properties on strain rate and temperature are discussed for different morphologies. A diblock copolymer with a polystyrene content of 76% PS reveals hexagonally packed PBMA−cylinder, and the tensile strength, strain at break, and Young's modulus exceed the values of pure polystyrene at all measured strain rates. The interesting properties of PS-b-PBMA diblock copolymers are discussed with respect to the phase behavior, interface formation, and chain conformation.

Nylon-6 is widely used as an engineering plastic. Compared to other synthetic polymers, nylon-6 absorps significant amounts of water. Although the typical sorbed amounts and diffusivity of water are well-known, less is known about the relation between the diffusivity and the water content. Attempts have been made in the past to obtain such relationship from moisture content profiles as measured with NMR imaging. However, these studies were mainly performed at high temperatures and without a proper calibration of the signal. In particular, at room temperature, far below the T g of dry nylon, plasticizing effects of water will result in a strong contribution of the polymer signal. Therefore, we have studied water uptake in 200 μm nylon-6 films in this temperature range near room temperature with NMR imaging. By calibrating the NMR signal with vapor sorption data, we were able to obtain moisture content profiles. A strongly nonlinear relation between the NMR signal and the moisture was observed at room temperature, which proves that contribution of the polymer to the NMR signal can neither be neglected nor assumed to be constant in time. Furthermore, glass transition temperature measurements combined with the water distribution provide plasticization profiles during water uptake. On the basis of the moisture content profiles, the moisture content dependency of the diffusion coefficient for water uptake is deduced through a Matano−Boltzmann analysis. This relation appeared to be highly nonlinear at room temperature. The self-diffusion coefficient was calculated through combination of the sorption-isotherm and the diffusion coefficient. Exposure of a nylon film to heavy water showed that water affects only a small fraction of the amorphous nylon phase. Water transport most likely occurs in this fraction of the amorphous phase. It is concluded that the heterogeneity of the amorphous phase is an important issue for a profound understanding of water transport in nylon-6 films. ■ INTRODUCTIONPolyamides, also known as nylons, are widely used as engineering plastic and textile fiber mainly due to their excellent properties. In particular, the mechanical properties are attractive for many applications and remain unaffected in a wide range of temperatures. Nylon is also easy to process, for example by extrusion molding, which is reflected in the large variety of geometries encountered in every day life.The chemical structure of nylons consists of amide groups separated by a number of methylene units. Therefore, a variety of polyamides exist, consisting of either one single α,ω aminoacid monomer like nylon-6 (PA6) and nylon-12 or two monomers, a dicarboxylic acid and a diamine like nylon 4.6 or 6.6. The number of successive carbon atoms in the polymer backbone between the amide groups is given by the index and influences material properties such a stiffness, melting point or water absorption.1 The latter feature is especially caused by the hydrophilic character of the amide functionality.Nylons absorb amounts of wat...

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