In contrast to all known shape memory polymers, the melting temperature of crystals in shape memory natural rubber (SMNR) can be greatly manipulated by the application of external mechanical stress. As shown previously, stress perpendicular to the prior programming direction decreases the melting temperature by up to 40 K. In this study, we investigated the influence of mechanical stress parallel to prior stretching direction during programming on the stability of the elongation-stabilizing crystals. It was found that parallel stress stabilizes the crystals, which is indicated by linear increase of the trigger temperature by up to 17 K. The crystal melting temperature can be increased up to 126.5 °C under constrained conditions as shown by X-ray diffraction measurements.
We found that constrained shape memory natural rubber (SMNR) generates mechanical stress when exposed to solvent vapor. When the solvent vapor is removed, the material reprograms itself. This process is reversible and the stress answer is proportional to the solvent vapor concentration. Further, the stress answer is specific to the solvent.
Lightly cross-linked natural rubber (NR, cis-1,4-polyisoprene) was found to be an exceptional cold programmable shape memory polymer (SMP) with strain storage of up to 1000%. These networks are stabilized by strain-induced crystals. Here, we explore the influence of mechanical stress applied perpendicular to the elongation direction of the network on the stability of these crystals. We found that the material recovers its original shape at a critical transverse stress. It could be shown that this is due to a disruption of the strain-stabilizing crystals, which represents a completely new trigger for SMPs. The variation of transverse stress allows tuning of the trigger temperature T(trig) (σ) in a range of 45 to 0 °C, which is the first example of manipulating the transition of a crystal-stabilized SMP after programming.
Generally reversible stimuli-responsive materials do not memorize the stimulus. In this study we describe an example in which stretched and constrained semi-crystalline polymer networks respond to solvent gases with stress and simultaneously memorize the concentration and the chemical nature of the solvent itself in their microstructure. This written solvent signature can even be deleted by temperature.
Typical shape memory polymers are hot-programmed and show a shape transition over a broad temperature range of 10 K and more. Cold-programmed shape memory natural rubber (SMNR) recovers more than 80% of its original shape within 1 K. The trigger point can be increased upon aging the stretched SMNR over several weeks without losing the narrow trigger range. This process can be accelerated by treatment of the stretched SMNR with nonaffine solvent vapors. Affine solvent vapors of low concentrations afford higher trigger points than that achieved by aging. This way, even higher cross-linked natural rubber can be cold-programmed.
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