On the Benefits of Rubbing Salt in the Cut: Self‐Healing of Saloplastic PAA/PAH Compact Polyelectrolyte Complexes

Reisch, Andreas; Roger, Émilie; Phoeung, Thida; Antheaume, Cyril; Orthlieb, Camille; Boulmedais, Fouzia; Lavalle, Philippe; Schlenoff, Joseph B.; Frisch, Benoı̂t; Schaaf, Pierre

doi:10.1002/adma.201304991

Cited by 123 publications

(155 citation statements)

References 34 publications

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“…Here, we focused on the relatively stable PIC gels . Benefitting from the charge interaction features, the PIC hydrogels show an impressive performance in their dynamic properties, including self‐healing, reprocessability, and saline responsiveness, and they also share the typical mechanical properties of other physically cross‐linked tough hydrogels, such as enhanced toughness, fatigue resistance, and deformation‐recovery abilities . However, compared to the instant one‐step preparation of other hydrogels, the preparation of these PIC hydrogels are hindered by a 1‐week dialysis process after polymerization to remove the residual salt and toughen the hydrogel …”

Section: Methodsmentioning

confidence: 99%

One‐Step Preparation of Tough and Self‐Healing Polyion Complex Hydrogels with Tunable Swelling Behaviors

Tang

Yang

et al. 2018

Macromol. Rapid Commun.

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Polyion complex (PIC) hydrogels formed by charge attraction of opposite charged polymers have received unique research interest. Their conventional preparation method, with a large amount of residual salt after polymerization, requires a long‐term dialysis treatment to remove the salt and toughen the gel. Here, a promising strategy for the one‐step preparation of tough PIC hydrogels without dialysis after polymerization is provided. Bicarbonate and proton ions are selected as the counter ions of the cationic monomer and anionic polymers, respectively. By a CO2‐generating reaction between the counter ions, the residual salt is removed before polymerization, and thus, a PIC hydrogel with tough mechanical performance can be obtained instantly without dialysis. Due to the absence of dialysis, the tough hydrogel can be formed with a wide range of ratios for the oppositely charged polymer with distinct swelling behaviors from non‐swelling to super‐swelling. This tunable swelling behavior shows the possibility for shape‐morphing systems from this one‐step method.

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Section: Methodsmentioning

confidence: 99%

One‐Step Preparation of Tough and Self‐Healing Polyion Complex Hydrogels with Tunable Swelling Behaviors

Tang

Yang

et al. 2018

Macromol. Rapid Commun.

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“…Examples of ionic interactions utilized in self‐healing: a) polyethylene‐ co ‐methacrylic acid) (EMMA); b‐1) Poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) forming compact polyelectrolyte complexes (CoPECs); b‐2) poly(3‐(methacryloylamino)propyl‐trimethylammonium chloride)/poly(sodium p ‐styrenesulphonate); b‐3) poly(allylamine hydrochloride) (PAH)/tripolyphosphate (TPP); c) acotinates/N″″‐tetramethyl‐1,3‐ propanediammonium; d) poly(carboxybetaine acrylamide) (PCB); e) alginate/Ca 2+ . Reproduced with permission .…”

Section: Ionic Interactionsmentioning

confidence: 99%

Self‐Healing of Polymers via Supramolecular Chemistry

Yang

Urban

2018

Adv Materials Inter

156

117

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rearrangements. While one challenge is to incorporate chemical modifications enabling chemical bond reformations, equally important is the coordination of chemical events with polymer network physical changes within interfacial regions resulting from mechanical damage.Recent studies suggested that two types of dynamic bonds are highly attractive to achieve self-healing in polymers: reversible covalent bonds and supramolecular chemistry. Reversible covalent bonds offer higher bonding energies, allowing the material to regain physical properties similar to conventional polymers prior to damage. Advantages and disadvantages of reversible covalent bonding were summarized in several review articles. [5] Self-healing involving dynamic dissociation/association using supramolecular chemistry offers fast reversibility under ambient conditions reaching exceptionally quickly equilibrium state, bonding directionality, and remarkable sensitivity. Since broad-range of network structures can be obtained via supramolecular interactions, applications in soft electronics, sensing, biomedical technologies, 3-4D printing, and reprocessable materials are highly attractive and may open many new technological opportunities (Figure 1). Mechanical integrity using supramolecular chemistry is achieved by the formation of multiple noncovalent interactions between multiple associative groups covalently attached to polymer side chain or chain ends of macromolecular building blocks. These interactions include H-bonding, metal-ligand complexation, hostguest, ionic interactions, π-π stacking, and hydrophobic interactions. They are depicted in Figure 1. In contrast to covalent rebonding, mechanical properties of supramolecular polymer networks are achieved by the presence of these secondary interactions forming noncovalent crosslinks, which bind liquid-like building blocks into plastic or rubbery polymers in hydrated and nonhydrated states. The dynamic nature of these noncovalent bonds provides an opportunity for self-healing attributed to reassociation of supramolecular components, similar to secondary interactions found in living systems that regulate many living functions. The rule of thumb in designing these networks is that the degree of association is determined by the equilibrium constant (K a ) values, whereas dynamics is driven by rate constants of the association-dissociation reactions, k a and k d , respectively. [6] Molecular structural and electronic features along with network heterogeneities are of particular importance in these networks. Mechanical strength and elasticity of supramolecular polymers are determined by not only the K a values, but also stacking and clustering of the associative groups which may result in heterogeneities leading to the Recent advances of supramolecular chemistry utilized in the development of self-healing polymers have revealed that the rate and equilibrium constants of bond dissociation/re-association, bonding directionality, chain relaxation time, decay rate of chain relaxation after damage, and clu...

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“…Noncovalent bonding, including ionic bonding, hydrogen bonding, supramolecular interactions, metal–ligand coordination, and π–π interactions significantly broaden the scope of self‐healing materials, making highly reversible and ambient healing possible. Fast and efficient healing originates from high mobility polymer chains, which is determined by free volume and interaction strength.…”

Section: Introductionmentioning

confidence: 99%

“…The free volume and chain mobility of ionically bonded polymers are strongly influenced by ionic strength, pH, and water fraction, which could be used as stimuli to trigger healing. Rapid and efficient self‐healing behavior was observed in an ionically bonded complex of polyacrylic acid (PAA) and poly(allylamine hydrochloride) using sodium chloride as a promoter . The porous and loosely packed structure made this complex less robust than more dense layer‐by‐layer (LbL) polyelectrolyte assemblies.…”

Section: Introductionmentioning

confidence: 99%

Fast Self‐Healing of Polyelectrolyte Multilayer Nanocoating and Restoration of Super Oxygen Barrier

Song

Meyers

Gerringer

et al. 2017

Macromol. Rapid Commun.

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A self-healable gas barrier nanocoating, which is fabricated by alternate deposition of polyethyleneimine (PEI) and polyacrylic acid (PAA) polyelectrolytes, is demonstrated in this study. This multilayer film, with high elastic modulus, high glass transition temperature, and small free volume, has been shown to be a super oxygen gas barrier. An 8-bilayer PEI/PAA multilayer assembly (≈700 nm thick) exhibits an oxygen transmission rate (OTR) undetectable to commercial instrumentation (<0.005 cc (m d atm )). The barrier property of PEI/PAA nanocoating is lost after a moderate amount of stretching due to its rigidity, which is then completely restored after high humidity exposure, therefore achieving a healing efficiency of 100%. The OTR of the multilayer nanocoating remains below the detection limit after ten stretching-healing cycles, which proves this healing process to be highly robust. The high oxygen barrier and self-healing behavior of this polymer multilayer nanocoating makes it ideal for packaging (food, electronics, and pharmaceutical) and gas separation applications.

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On the Benefits of Rubbing Salt in the Cut: Self‐Healing of Saloplastic PAA/PAH Compact Polyelectrolyte Complexes

Cited by 123 publications

References 34 publications

One‐Step Preparation of Tough and Self‐Healing Polyion Complex Hydrogels with Tunable Swelling Behaviors

One‐Step Preparation of Tough and Self‐Healing Polyion Complex Hydrogels with Tunable Swelling Behaviors

Self‐Healing of Polymers via Supramolecular Chemistry

Fast Self‐Healing of Polyelectrolyte Multilayer Nanocoating and Restoration of Super Oxygen Barrier

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