The past several years have witnessed significant advances in the field of shape memory polymers (SMPs) with the elucidation of new compositions for property tuning, the discovery of new mechanisms for shape fixing and recovery, and the initiation of phenomenological modeling. We critically review research findings on new shape memory polymers along these lines, emphasizing exciting progress in the areas of composites, novel recovery triggering, and new application developments. 445Annu. Rev. Mater. Res. 2009.39:445-471. Downloaded from www.annualreviews.org by NORTH CAROLINA STATE UNIVERSITY on 09/29/12. For personal use only.

Self-healing (SH) polymers are responsive polymeric materials that can repair mechanical damage such as cracks in an autonomous fashion. In most SH polymers studies reported to date, crack closure was either unaddressed or achieved by manual intervention. Here, we report a new strategy that utilizes shape memory (SM) to prepare novel SH polymers that are capable of simultaneously closing and rebonding cracks with a simple thermal trigger. This strategy, termed "shape memory assisted self-healing (SMASH)", is demonstrated in a blend system consisting of cross-linked poly(ε-caprolactone) network (n-PCL) with linear poly(ε-caprolactone) (l-PCL) interpenetrating the network, and exhibits a combination of SM response from the network component and SH capacity from the linear component. Thermomechanical analysis revealed that the thermoset, n-PCL, demonstrates reversible plasticity -a form of shape memory where large plastic deformation at room temperature is fully recoverable upon heating. This SM action assists to close any cracks formed during deformation and/or damage while l-PCL chains tackify the crack surfaces by diffusion to the free surface and ultimately across the area of damage during the same heating step as used for SM. In our study, we investigated the controlled damage and SMASH healing of blends with varying composition using tensile testing of essential work of fracture film specimens. The healing component, l-PCL used had a high M(w) (M(w) ∼65k g/mol) to enable re-entanglement after diffusion across the interface while the shape memory component, n-PCL was prepared from PCL telechelic diacrylates and a tetrathiol cross-linker, yielding excellent shape memory. We found excellent self-healing of films by the SMASH mechanism, with near complete healing for l-PCL contents exceeding 25 wt %. Applications are envisioned in the area of self-healing bladders, inflated structure membranes, and architectural building envelopes.

In this communication, we report the preparation and characterization of new shape memory assisted selfhealing (SMASH) coatings. The coatings feature a phaseseparated morphology with electrospun thermoplastic poly(εcaprolactone) (PCL) fibers randomly distributed in a shape memory epoxy matrix. Mechanical damage to the coating can be self-healed via heating, which simultaneously triggers two events: (1) the shape recovery of the matrix to bring the crack surfaces in spatial proximity, and (2) the melting and flow of the PCL fibers to rebond the crack. In controlled healing experiments, damaged coatings not only heal structurally, but also functionally by almost completely restoring the corrosion resistance. We envision the wide applicability of the SMASH concept in designing the next-generation self-healing materials.

In this paper, the fabrication and characterization of triple‐shape polymeric composites (TSPCs) that, unlike traditional shape memory polymers (SMPs), are capable of fixing two temporary shapes and recovering sequentially from the first temporary shape (shape 1) to the second temporary shape (shape 2), and eventually to the permanent shape (shape 3) upon heating, are reported. This is technically achieved by incorporating non‐woven thermoplastic fibers (average diameter ∼760 nm) of a low‐Tm semicrystalline polymer into a Tg‐based SMP matrix. The resulting composites display two well‐separated transitions, one from the glass transition of the matrix and the other from the melting of the fibers, which are subsequently used for the fixing/recovery of two temporary shapes. Three thermomechanical programming processes with different shape fixing protocols are proposed and explored. The intrinsic versatility of this composite approach enables an unprecedented large degree of design flexibility for functional triple‐shape polymers and systems.

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Nickel nanoparticles were prepared from the thermal decomposition of nickel(II) acetylacetonate in alkylamines and characterized by powder x-ray diffraction, transmission electron microscopy and magnetic measurement. The reaction temperature, heating rate and solvent type play an important role in the control over the crystalline phase. Depending on the reaction conditions, face-centered cubic (fcc) or hexagonal close-packed (hcp) nickel nanoparticles can be obtained. Monodisperse nickel nanoparticles were also obtained by introducing surfactants. The results of magnetic characterization showed that the magnetic properties of the hcp nickel nanoparticles are quite different from those of the fcc nickel nanoparticles.

In this paper, we report on the development of a new and broadly applicable strategy to produce thermally mendable polymeric materials, demonstrated with an epoxy/poly(-caprolactone) (PCL) phase-separated blend. The initially miscible blend composed of 15.5 wt % PCL undergoes polymerization-induced phase separation during cross-linking of the epoxy, yielding a "bricks and mortar" morphology wherein the epoxy phase exists as interconnected spheres (bricks) interpenetrated with a percolating PCL matrix (mortar). The fully cured material is stiff, strong, and durable. A heating-induced "bleeding" behavior was witnessed in the form of spontaneous wetting of all free surfaces by the molten PCL phase, and this bleeding is capable of repairing damage by crack-wicking and subsequent recrystallization with only minor concomitant softening during that process. The observed bleeding is attributed to volumetric thermal expansion of PCL above its melting point in excess of epoxy brick expansion, which we term differential expansive bleeding (DEB). In controlled thermal-mending experiments, heating of a cracked specimen led to PCL extrusion from the bulk to yield a liquid layer bridging the crack gap. Upon cooling, a "scar" composed of PCL crystals formed at the site of the crack, restoring a significant portion of the mechanical strength. When a moderate force was applied to assist crack closure, thermal-mending efficiencies exceeded 100%. We further observed that the DEB phenomenon enables strong and facile adhesion of the same material to itself and to a variety of materials, without any requirement for macroscopic softening or flow.