A review of shape memory alloy research, applications and opportunities

This article provides an up-to-date perspective on the use of anion-exchange membranes in fuel cells, electrolysers, redox flow batteries, reverse electrodialysis cells, and bioelectrochemical systems (e.g. microbial fuel cells). The aim is to highlight key concepts, misconceptions, the current state-of-the-art, technological and scientific limitations, and the future challenges (research priorities) related to the use of anion-exchange membranes in these energy technologies. All the references that the authors deemed relevant, and were available on the web by the manuscript submission date (30th April 2014), are included.

/pdf/anion-exchange-membranes-in-electrochemical-energy-systems-46uquenb56.pdf

Anion-exchange membranes in electrochemical energy systems

Supramolecular materials, dynamic materials by nature, are defined as materials whose components are bridged via reversible connections and undergo spontaneous and continuous assembly/disassembly processes under specific conditions. On account of the dynamic and reversible nature of noncovalent interactions, supramolecular polymers have the ability to adapt to their environment and possess a wide range of intriguing properties, such as degradability, shape-memory, and self-healing, making them unique candidates for supramolecular materials. In this critical review, we address recent developments in supramolecular polymeric materials, which can respond to appropriate external stimuli at the fundamental level due to the existence of noncovalent interactions of the building blocks.

Stimuli-responsive supramolecular polymeric materials.

In chemistry, some dynamic bonds can be selectively and reversibly broken and reformed in response to an environmental stimulus. This Review article discusses the incorporation of dynamic bonds, or interactions, in polymeric materials and the structural changes and macroscopic responses observed in the presence of different stimuli.

Using the dynamic bond to access macroscopically responsive structurally dynamic polymers

Shape memory polymers are materials that can memorize temporary shapes and revert to their permanent shape upon exposure to an external stimulus such as heat, light, moisture or magnetic field. Such properties have enabled a variety of applications including deployable space structures, biomedical devices, adaptive optical devices, smart dry adhesives and fasteners. The ultimate potential for a shape memory polymer, however, is limited by the number of temporary shapes it can memorize in each shape memory cycle and the ability to tune the shape memory transition temperature(s) for the targeted applications. Currently known shape memory polymers are capable of memorizing one or two temporary shapes, corresponding to dual- and triple-shape memory effects (also counting the permanent shape), respectively. At the molecular level, the maximum number of temporary shapes a shape memory polymer can memorize correlates directly to the number of discrete reversible phase transitions (shape memory transitions) in the polymer. Intuitively, one might deduce that multi-shape memory effects are achievable simply by introducing additional reversible phase transitions. The task of synthesizing a polymer with more than two distinctive and strongly bonded reversible phases, however, is extremely challenging. Tuning shape memory effects, on the other hand, is often achieved through tailoring the shape memory transition temperatures, which requires alteration in the material composition. Here I show that the perfluorosulphonic acid ionomer (PFSA), which has only one broad reversible phase transition, exhibits dual-, triple-, and at least quadruple-shape memory effects, all highly tunable without any change to the material composition.

Tunable polymer multi-shape memory effect

Shape-Memory Effects in Polymer Networks Containing Reversibly Associating Side-Groups

Polymers containing hydrogen-bonding side groups (HBGs) can form transient supramolecular networks that exhibit technologically useful viscoelastic properties. Here, we investigate how dynamic behavior of functional poly(n-butyl acrylate) melts and cross-linked networks is influenced by different HBGs. Random copolymers containing weak and strong HBGs were synthesized and subjected to thermal and dynamic mechanical analysis. The glass transition temperature (Tg) increased nearly linearly with the HBG concentration, and this effect was similar for both weak and strong binding groups. Copolymers containing weak HBGs behaved as unentangled melts and exhibited higher storage and loss modulus with increasing amounts of binding group. In contrast, copolymers containing strong HBGs behaved like entangled networks. Flow activation energies increased linearly with comonomer content; and, for weak hydrogen-bonding groups, they depended only on the departure from Tg. Similar behavior was observed in cross-linked fil...

The Influence of Hydrogen Bonding Side-Groups on Viscoelastic Behavior of Linear and Network Polymers

We demonstrate a single-phase, two-way shape actuator that, in the absence of an external load, elongates upon cooling and reversibly contracts upon heating. In a simple and straightforward process, a partially cross-linked, semicrystalline poly(e-caprolactone) (PCL) network is melted, stretched to several hundred percent strain, and further cross-linked. Upon removal of the applied load, the elastic double network adopts a “state-of-ease” that retains part of its former strain. When cooled, internal stress-induced crystallization causes further elongation of configurationally biased chains. When heated, crystallites melt, and the sample returns to its equilibrium state-of-ease. Under optimized conditions, reversible actuation >15% strain can be reproducibly achieved, and samples can be cycled multiple times with highly uniform actuation with no observable creep. The mechanism behind such actuation was further confirmed via calorimetry and X-ray scattering.

https://pubs.acs.org/doi/pdf/10.1021/mz500773v

Shape Actuation via Internal Stress-Induced Crystallization of Dual-Cure Networks

Energy Storage Capacity of Shape-Memory Polymers

Controlling network architecture and chain connectivity is critical to understanding elastic energy storage and improving performance of shape-memory polymers. Acrylate-terminated poly(caprolactones) were converted into thermoset networks by three different reactions: conventional free radical polymerization, radical-induced coupling with multifunctional thiols, and base-catalyzed Michael addition with multifunctional thiols. The highly efficient thiol–acrylate coupling reaction ensures that the molecular weight between cross-links is uniform, resulting in tougher, more elastic materials with a high degree of crystallinity and outstanding shape-memory properties. Elastomers can be cold drawn to achieve several hundred percent of strain, and upon heating, nearly complete shape recovery is observed. Shape fixity upon cold drawing is correlated to the degree of strain-induced crystallization which is influenced by the draw rate and stress treatment immediately following cold drawing. Slow unloading of sample...

Mitchell Anthamatten

Papers

Shape-Memory Effects in Polymer Networks Containing Reversibly Associating Side-Groups

The Influence of Hydrogen Bonding Side-Groups on Viscoelastic Behavior of Linear and Network Polymers

Shape Actuation via Internal Stress-Induced Crystallization of Dual-Cure Networks

Energy Storage Capacity of Shape-Memory Polymers

Well-Defined Shape-Memory Networks with High Elastic Energy Capacity