Carbon nanotubes (CNTs) are under intense investigation in materials science owing to their potential for modifying the electrical conductivity sigma, shear viscosity eta, and other transport properties of polymeric materials. These particles are hybrids of filler and nanoscale additives because their lengths are macroscopic whereas their cross-sectional dimensions are closer to molecular scales. The combination of extended shape, rigidity and deformability allows CNTs to be mechanically dispersed in polymer matrices in the form of disordered 'jammed' network structures. Our measurements on representative network-forming multiwall nanotube (MWNT) dispersions in polypropylene indicate that these materials exhibit extraordinary flow-induced property changes. Specifically, sigma and eta both decrease strongly with increasing shear rate, and these nanocomposites exhibit impressively large and negative normal stress differences, a rarely reported phenomenon in soft condensed matter. We illustrate the practical implications of these nonlinear transport properties by showing that MWNTs eliminate die swell in our nanocomposites, an effect crucial for their processing.
Among the novel chemical and physical attributes of single-wall carbon nanotubes (SWCNTs), the optical properties are perhaps the most compelling. Although much is known about how such characteristics depend on nanotube chirality and diameter, relatively little is known about how the optical response depends on length, the next most obvious and fundamental nanotube trait. We show here that the intrinsic optical response of single-wall carbon nanotubes exhibits a strong dependence on nanotube length, and we offer a simple explanation that relates this behavior to the localization of a bound exciton along the length of a nanotube. The results presented here suggest that, for a given volume fraction, the longest nanotubes display significantly enhanced absorption, near-infrared fluorescence, and Raman scattering, which has important practical implications for potential applications that seek to exploit the unique optical characteristics of SWCNTs.
Material extrusion (ME)2 is a layer-by-layer additive manufacturing process that is now used in personal and commercial production where prototyping and customization are required. However, parts produced from ME frequently exhibit poor mechanical performance relative to those from traditional means; moreover, fundamental knowledge of the factors leading to development of inter-layer strength in this highly non-isothermal process is limited. In this work, we seek to understand the development of inter-layer weld strength from the perspective of polymer interdiffusion under conditions of rapidly changing mobility. Our framework centers around three interrelated components: in-situ thermal measurements (via infrared imaging), temperature dependent molecular processes (via rheology), and mechanical testing (via mode III fracture). We develop the concept of an equivalent isothermal weld time and test its relationship to fracture energy. For the printing conditions studied the equivalent isothermal weld time for Tref = 230 °C ranged from 0.1 ms to 100 ms. The results of these analysis provide a basis for optimizing inter-layer strength, the limitations of the ME process, and guide development of new materials.
We have discovered a droplet-string transition in concentrated polymer blends which occurs when the size of the dispersed droplets becomes comparable to the gap width between the shearing surfaces. The transition is abrupt and proceeds via the coalescence of droplets in a four-stage kinetic process. Once formed, the strings are stable and exhibit pronounced hysteresis. The string state is stabilized by a suppression of the Rayleigh-Tomotika instability due to both finite size effects and to the shear-induced advection of small-amplitude disturbances.
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