Superheated Rubber for Cold Storage

Stimuli-responsive (active) materials undergo large-scale shape or property changes in response to an external stimulus such as stress, temperature, light or pH. Technological uses range from durable, shape-recovery eye-glass frames, to temperature-sensitive switches, to the generation of stress to induce mechanical motion. Here, we demonstrate that the uniform dispersion of 1-5 vol.% of carbon nanotubes in a thermoplastic elastomer yields nanocomposites that can store and subsequently release, through remote means, up to 50% more recovery stress than the pristine resin. The anisotropic nanotubes increase the rubbery modulus by a factor of 2 to 5 (for 1-5 vol.%) and improve shape fixity by enhancing strain-induced crystallization. Non-radiative decay of infrared photons absorbed by the nanotubes raises the internal temperature, melting strain-induced polymer crystallites (which act as physical crosslinks that secure the deformed shape) and remotely trigger the release of the stored strain energy. Comparable effects occur for electrically induced actuation associated with Joule heating of the matrix when a current is passed through the conductive percolative network of the nanotubes within the resin. This unique combination of properties, directly arising from the nanocomposite morphology, demonstrates new opportunities for the design and fabrication of stimuli-responsive polymers, which are otherwise not available in one material system.

Material scientists predict a prominent role in the future for self-repairing and intelligent materials. Throughout the last few years, this concept has found growing interest as a result of the rise of a new class of polymers. These so-called shape-memory polymers by far surpass well-known metallic shape-memory alloys in their shape-memory properties. As a consequence of the relatively easy manufacture and programming of shape-memory polymers, these materials represent a cheap and efficient alternative to well-established shape-memory alloys. In shape-memory polymers, the consequences of an intended or accidental deformation caused by an external force can be ironed out by heating the material above a defined transition temperature. This effect can be achieved because of the given flexibility of the polymer chains. When the importance of polymeric materials in our daily life is taken into consideration, we find a very broad, additional spectrum of possible applications for intelligent polymers that covers an area from minimally invasive surgery, through high-performance textiles, up to self-repairing plastic components in every kind of transportation vehicles.

A new method of estimating the equilibrium melting temperature, T m , of a polymer is described, and applied to polychlorotrifluoroethylene (PCTFE). Experimentally determined values of the so-called observed melting point, T m ′ ( obs ) , are plotted as a function of the isothermal crystallization temperature, T x . When freed of secondary effects, such as recrystallization, the data fit a straight line of positive slope on a T m ′ ( obs ) versus T x plot, T x being the abscissa. This line is then extrapolated to its intersection with the line T m ′ ( obs ) = T x . The temperature at this intersection is T m . This intersection is at 224 °C for PCTFE, and T m is quoted as 224 ± 1 °C. (The highest melting point actually attained for a specimen was 218.2 °C.) The value of T m estimated using the extrapolation procedure is compared with that estimated using the customary method of slow stepwise warming. A theoretical justification is given for making the type of plot mentioned above. The most important assumption used in the theory is that one of the dimensions of the growing crystal retains a value rather close to that of the appropriate growth nucleus during an isothermal crystallization, the other two dimensions being large in comparison. Combination of this with the fact that the relevant dimension of the growth nucleus will vary as the reciprocal of the degree of supercooling leads to the prediction of melting points that increase linearly with crystallization temperature. The assumption that one of the dimensions of the crystal retains a value fairly close to that of a growth nucleus can readily be justified on the basis of polymer crystal growth with chain folds. Its justification in the case of the customary bundlelike mode of crystallization is less clear. It is demonstrated experimentally that even the largest detectible crystals in PCTFE are only about 70 percent thicker than a primary nucleus, when secondary effects are minimized. The application of the theory to systems other than PCTFE is discussed briefly, and some preliminary measurements on polyethylene mentioned. Some points relating to the shape of the melting curves of highly crystalline polymers are also brought out.