The merits of thiol-click chemistry and its potential for making new forays into chemical synthesis and materials applications are described Since thiols react to high yields under benign conditions with a vast range of chemical species, their utility extends to a large number of applications in the chemical, biological, physical, materials and engineering fields This critical review provides insight into emerging venues for application as well as new mechanistic understanding of this exceptional chemistry in its many forms (81 references)

Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis

Self-healing polymers and fiber-reinforced polymer composites possess the ability to heal in response to damage wherever and whenever it occurs in the material. This phenomenal material behavior is...

Self-Healing Polymers and Composites

Inspired by the unique and efficient wound healing processes in biological systems, several approaches to develop synthetic polymers that can repair themselves with complete, or nearly complete, autonomy have recently been developed. This review aims to survey the rapidly expanding field of self-healing polymers by reviewing the major successful autonomic repairing mechanisms developed over the last decade. Additionally, we discuss several issues related to transferring these self-healing technologies from the laboratory to real applications, such as virgin polymer property changes as a result of the added healing functionality, healing in thin films v. bulk polymers, and healing in the presence of structural reinforcements.

Self-healing polymers and composites

Engineering applications of synthetic polymers are widespread due to their availability, processability, low density, and diversity of mechanical properties (Figure 1a). Despite their ubiquitous nature, modern polymers are evolving into multifunctional systems with highly sophisticated behavior. These emergent functions are commonly described as “smart” characteristics whereby “intelligence” is rooted in a specific response elicited from a particular stimulus. Materials that exhibit stimuli-responsive functions thus achieve a desired output (O, the response) upon being subjected to a specific input (I, the stimulus). Given that mechanical loading is inevitable, coupled with the wide range of mechanical properties for synthetic polymers, it is not surprising that mechanoresponsive polymers are an especially attractive class of smart materials. To design materials with stimuli-responsive functions, it is helpful to consider the I-O relationship as an energy transduction process. Achieving the desired I-O linkage thus becomes a problem in finding how to transform energy from the stimulus into energy that executes the desired response. The underlying mechanism that forms this I-O coupling need not be a direct, one-step transduction event; rather, the overall process may proceed through a sequence of energy transduction steps. In this regard, the network of energy transduction pathways is a useful roadmap for designing stimuli-responsive materials (Figure 1b). It is the purpose of this review to broadly survey the mechanical to chemical * To whom correspondence should be addressed. Phone: 217-244-4024. Fax: 217-244-8024. E-mail: jsmoore@illinois.edu. † Department of Chemistry and Beckman Institute. ‡ Department of Materials Science and Engineering and Beckman Institute. § Department of Aerospace Engineering and Beckman Institute. Chem. Rev. XXXX, xxx, 000–000 A

Mechanically-induced chemical changes in polymeric materials

Inspired by nature, self-healing materials represent the forefront of recent developments in materials chemistry and engineering. This review outlines the recent advances in the field of self-healing polymers. The first part discusses thermodynamic requirements for self-healing networks in the context of conformation changes that contribute to the Gibbs free energy. The chain flexibility significantly contributes to the entropy changes, whereas the heat of reaction and the external energy input are the main contributors to enthalpy changes. The second part focuses on chemical reactions that lead to self-healing, and the primary classes are the covalent bonding, supramolecular assemblies, ionic interactions, chemo-mechanical self-healing, and shape memory polymers. The third part outlines recent advances using encapsulation, remote self-healing and the role of shape memory polymers. Recent developments in the field of self-healing polymers undeniably indicate that the main challenge will be the designing of high glass transition (Tg) functional materials, which also exhibit stimuli-responsive attributes. Build-in controllable hierarchical heterogeneousness at various length scales capable of remote self-healing by physical and chemical responses will be essential in designing future materials of the 21st century.

Self-healing polymeric materials

A self-healing system based on conventional epoxy resin was successfully developed in this work. Epoxy and its hardener mercaptan were microencapsulated as two-component healing agent, and then the microcapsules were embedded in epoxy matrix. Attractive healing effect can be acquired at low capsule content (e.g., 43.5% healing efficiency with 1 wt % capsules and 104.5% healing efficiency with 5 wt % capsules at 20 °C for 24 h). Since only a few healant proves to be sufficient for crack repairing, a better balance between strength and toughness restoration can thus be achieved. As a result of high flowability, fast consolidation, and molecular miscibility of the released healing agent consisting of epoxy and mercaptan, self-healing was allowed to proceed rapidly offering satisfactory repair effectiveness.

Self-Healing Polymeric Materials Using Epoxy/Mercaptan as the Healant

To provide epoxy resin with crack healing capability, an epoxy containing both furan and epoxide groups, N,N-diglycidyl-furfurylamine (DGFA), was synthesized through a two-step approach. When it reacted with N,N′-(4,4′-diphenylmethane) bismaleimide (DPMBMI) and methylhexahydrophthalic anhydride (MHHPA), respectively, a crosslinked polymer with two types of intermonomer linkage was yielded. That is, thermally reversible Diels–Alder (DA) bonds from the reaction between furan and maleimide groups, and thermally stable bonds from the reaction between epoxide and anhydride groups. In this way, cured DGFA possessed not only similar mechanical properties as commercial epoxy, but also thermal remendability that enabled elimination of cracks. The latter function took effect as a result of successive retro-DA and DA reactions, which led to crack healing in a controlled manner through chain reconnection.

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A thermally remendable epoxy resin

The present paper is devoted to preparation of intrinsic self-healing polymeric materials used for structural applications. The authors introduced a novel healing chemistry based on dynamically rev...

Yan Chao Yuan

Papers

Self-Healing Polymeric Materials Using Epoxy/Mercaptan as the Healant

A thermally remendable epoxy resin

Self-Healing of Polymers via Synchronous Covalent Bond Fission/Radical Recombination

Preparation and characterization of microencapsulated polythiol

Self-healing epoxy based on cationic chain polymerization