Double-network (DN) gels have drawn much attention as an innovative material having both high water content (ca. 90 wt%) and high mechanical strength and toughness. DN gels are characterized by a special network structure consisting of two types of polymer components with opposite physical natures: the minor component is abundantly cross-linked polyelectrolytes (rigid skeleton) and the major component comprises of poorly cross-linked neutral polymers (ductile substance). The former and the latter components are referred to as the first network and the second network, respectively, since the synthesis should be done in this order to realize high mechanical strength. For DN gels synthesized under suitable conditions (choice of polymers, feed compositions, atmosphere for reaction, etc.), they possess hardness (elastic modulus of 0.1–1.0 MPa), strength (failure tensile nominal stress 1–10 MPa, strain 1000–2000%; failure compressive nominal stress 20–60 MPa, strain 90–95%), and toughness (tearing fracture energy of 100∼1000 J m−2). These excellent mechanical performances are comparable to that of rubbers and soft load-bearing bio-tissues. The mechanical behaviors of DN gels are inconsistent with general mechanisms that enhance the toughness of soft polymeric materials. Thus, DN gels present an interesting and challenging problem in polymer mechanics. Extensive experimental and theoretical studies have shown that the toughening of DN gel is based on a local yielding mechanism, which has some common features with other brittle and ductile nano-composite materials, such as bones and dentins.

Why are double network hydrogels so tough

Phase change materials for thermal energy storage

In the past few years, spiropyran has emerged as the molecule-of-choice for the construction of novel dynamic materials. This unique molecular switch undergoes structural isomerisation in response to a variety of orthogonal stimuli, e.g. light, temperature, metal ions, redox potential, and mechanical stress. Incorporation of this switch onto macromolecular supports or inorganic scaffolds allows for the creation of robust dynamic materials. This review discusses the synthesis, switching conditions, and use of dynamic materials in which spiropyran has been attached to the surfaces of polymers, biomacromolecules, inorganic nanoparticles, as well as solid surfaces. The resulting materials show fascinating properties whereby the state of the switch intimately affects a multitude of useful properties of the support. The utility of the spiropyran switch will undoubtedly endow these materials with far-reaching applications in the near future.

/pdf/spiropyran-based-dynamic-materials-4c1onvrhup.pdf

Spiropyran-based dynamic materials

Radical addition-fragmentation chemistry in polymer synthesis

Oil spills and industrial organic pollutants have induced severe water pollution and threatened every species in the ecological system. To deal with oily water, special wettability stimulated materials have been developed over the past decade to separate oil-and-water mixtures. Basically, synergy between the surface chemical composition and surface topography are commonly known as the key factors to realize the opposite wettability to oils and water and dominate the selective wetting or absorption of oils/water. In this review, we mainly focus on the development of materials with either super-lyophobicity or super-lyophilicity properties in oil/water separation applications where they can be classified into four kinds as follows (in terms of the surface wettability of water and oils): (i) superhydrophobic and superoleophilic materials, (ii) superhydrophilic and under water superoleophobic materials, (iii) superhydrophilic and superoleophobic materials, and (iv) smart oil/water separation materials with switchable wettability. These materials have already been applied to the separation of oil-and-water mixtures: from simple oil/water layered mixtures to oil/water emulsions (including oil-in-water emulsions and water-in-oil emulsions), and from non-intelligent materials to intelligent materials. Moreover, they also exhibit high absorption capacity or separation efficiency and selectivity, simple and fast separation/absorption ability, excellent recyclability, economical efficiency and outstanding durability under harsh conditions. Then, related theories are proposed to understand the physical mechanisms that occur during the oil/water separation process. Finally, some challenges and promising breakthroughs in this field are also discussed. It is expected that special wettability stimulated oil/water separation materials can achieve industrial scale production and be put into use for oil spills and industrial oily wastewater treatment in the near future.

Biomimetic super-lyophobic and super-lyophilic materials applied for oil/water separation: a new strategy beyond nature

Autonomous self-healing of poly(acrylic acid) hydrogels induced by the migration of ferric ions

Redox-responsive gel-sol/sol-gel transition in aqueous PAA system containing Fe(III)-citrate complex was realized by switching the redox states of Fe(III)/F(II) ions conjugated with photoreduction and oxidation. This reversible transition can be indicated chromatically by the Fe(III) ions and repeated many times as long as there is sufficient citric acid.

Redox-responsive gel-sol/sol-gel transition in poly(acrylic acid) aqueous solution containing Fe(III) ions switched by light.

http://www.becergroup.sems.qmul.ac.uk/publications/papers/becer_030.pdf

Investigation into thiol-(meth)acrylate Michael addition reactions using amine and phosphine catalysts

Chitosan without hydrophobic modification is not a good emulsifier itself. However, it has a pH-tunable sol–gel transition due to free amino groups along its backbone. In the present work, a simple reversible Pickering emulsion system based on the pH-tunable sol–gel transition of chitosan was developed. At pH > 6.0, as adjusted by NaOH, chitosan was insoluble in water. Chitosan nanoparticles or micrometer-sized floccular precipitates were formed in situ. These chitosan aggregates could adsorb at the interface of oil and water to stabilize the o/w emulsions, so-called Pickering emulsions. At pH < 6.0, as adjusted by HCl, chitosan was soluble in water. Demulsification happened. Four organic solvents (liquid paraffin, n-hexane, toluene, and dichloromethane) were chosen as the oil phase. Reversible emulsions were formed for all four oils. Chitosan-based Pickering emulsions could undergo five cycles of emulsification–demulsification with only a slight increase in the emulsion droplet size. They also had good l...

Zhen Tong

Papers

Autonomous self-healing of poly(acrylic acid) hydrogels induced by the migration of ferric ions

Redox-responsive gel-sol/sol-gel transition in poly(acrylic acid) aqueous solution containing Fe(III) ions switched by light.

Investigation into thiol-(meth)acrylate Michael addition reactions using amine and phosphine catalysts

Simple, reversible emulsion system switched by pH on the basis of chitosan without any hydrophobic modification.

Combination of adsorption by porous CaCO3 microparticles and encapsulation by polyelectrolyte multilayer films for sustained drug delivery.