Hugh R. Brown

Progress toward robust polymer hydrogels

In this review we highlight new developments in tough hydrogel materials in terms of their enhanced mechanical performance and their corresponding toughening mechanisms. These mechanically robust hydrogels have been developed over the past 10 years with many now showing mechanical properties comparable with those of natural tissues. By first reviewing the brittleness of conventional synthetic hydrogels, we introduce each new class of tough hydrogel: homogeneous gels, slip-link gels, double-network gels, nanocomposite gels and gels formed using poly-functional crosslinkers. In each case we provide a description of the fracture process that may be occurring. With the exception of double network gels where the enhanced toughness is quite well understood, these descriptions remain to be confirmed. We also introduce material property charts for conventional and tough synthetic hydrogels to illustrate the wide range of mechanical and swelling properties exhibited by these materials and to highlight links between these properties and the network topology. Finally, we provide some suggestions for further work particularly with regard to some unanswered questions and possible avenues for further enhancement of gel toughness.

Adhesion and Fracture of Interfaces Between Immiscible Polymers: from the Molecular to the Continuum Scal

In order to obtain a measurable fracture toughness, a joint between two immiscible polymer glasses must be able to transfer mechanical stress across the interface. This stress transfer capability is very weak for narrow interfaces and a significant reinforcement can be achieved, either by the use of connecting chains (block copolymers), or by a broadening of the interface (random copolymers). In both cases, the stress is transferred by entanglements between polymer chains. The molecular criteria for efficient stress transfer, by connecting chains and by broad interfaces, are reviewed here with a special emphasis on the role of the molecular architecture (diblock, triblock or random copolymers) and molecular weight of the chains present at the interface. Recent theoretical developments in the relationship between macroscopic fracture toughness and interfacial stress transfer are also discussed, and the essential role of bulk plastic deformation properties of the polymers on either side of the interface are specifically addressed.

Jellyfish gel and its hybrid hydrogels with high mechanical strength

The fabrication of hydrogels with well-defined structure and high mechanical strength has become a challenging and fascinating topic. The aim of this study is to develop a new method for fabricating hydrogels with high mechanical strength by utilizing the well-developed structure of biological gels. We firstly studied the mechanical properties and microstructure of a biological gel—the mesogloea of edible jellyfish Rhopilema esculenta Kishinouye (JF gel). JF gel has much higher mechanical strength than normal synthetic hydrogels due to its layered porous structure with pore walls consisting of nano-structured layers and fibers. We have also synthesized hydrogels by radiation-induced polymerization and crosslinking and found that they are distinctly stronger than those produced by the classical thermal polymerization using a crosslinking agent. When a synthetic gel is incorporated into JF gel by the radiation-induced polymerization and crosslinking of a hydrophilic monomer, a novel type of hybrid hydrogel with very high mechanical strength results. The compressive and tensile strengths of the hybrid hydrogels are generally several times to more than ten times higher than those of JF gel and the corresponding component synthetic gels. The hybrid gels combine the well-developed structure of biological jellyfish gel and the unique microstructure of the synthetic gel produced by the radiation method, and strong interactions between the two networks are formed.

Interactions affecting the mechanical properties of macromolecular microsphere composite hydrogels.

Macromolecular microsphere composite (MMC) hydrogel is a kind of tough hydrogel fabricated by using peroxidized macromolecular microspheres as polyfunctional initiating and cross-linking centers (PFICC). The contribution of chemical cross-linking (covalent bonding) and physical cross-linking (chain entanglement and hydrogen bonding) to the mechanical properties are understood by testing the hydrogels, which were swollen in water or aqueous urea solutions to different water contents. The as-prepared MMC gels exhibited moderate moduli (60-270 kPa), high fracture tensile stresses (up to 0.54 MPa), high extensibilities (up to 2500%), and high fracture energies (270-770 J m(-2)). The moduli of the swollen gels decrease dramatically, but there are no significant changes in fracture tensile strength and fracture strain, even slight increases. More interestingly, the swollen gels show much-enhanced fracture energies, higher than 2000 J m(-2). A gradual decrease in the hysteresis ratio and residual strain is also found in the cyclic tensile testing of the hydrogels that were swollen to different water contents. The covalent bonding determines the tensile strength and fracture energy of the MMC gels, whereas the physical entanglement and hydrogen bonding among the polymer chains contributes mainly to the modulus of the MMC gels, and they are also the main reason for the presence of hysteresis in the loading-unloading cycles.

Mechanism of electropolymerisation of methyl methacrylate and glycidyl acrylate on stainless steel

An aqueous based technique for producing uniform, thin, passive films of poly(methyl methacrylate) (PMMA) and poly(glycidyl acrylate) (PGA) on stainless steel electrodes has been developed. A cathodic free radical polymerisation mechanism is proposed based upon the results of cyclic voltammetry (CV), mechanistic electro-polymerisation and gel permeation chromatography (GPC) experiments. The polymerisation yield was increased by a synergistic relationship between sulphuric acid and potassium persulphate initiators, proposed to involve the formation of long-lived radical species. Termination reactions are believed to be inhibited by the formation of co-ordination complexes between the growing polymer chain and sulphuric acid. The mechanism accounts for the broad molecular weight distribution, cross-linking and post-electrolysis polymerisation, where polymer continued to form after the current flow ceased.

Chain entanglements and fracture energy in interfaces between immiscible polymers

It is a very well-known experimental fact that the toughness of interfaces obtained by joining pairs of immiscible glassy polymers is strongly correlated to the interfacial width. Several models have been proposed in the literature to estimate the fracture energy of these interfaces, but the agreement displayed with the experimental data cannot be considered satisfactory. In this paper a new model is proposed for polymers with molecular weight higher than the critical value for the onset of entanglements. The model is based on a precise and realistic calculation of the areal density of entangled strands across the interface, that is the crucial parameter determining the toughness of the glassy joints. In this paper a new fracture regime is also introduced, called “partial crazing,” corresponding to a situation where, due to the fact that some of the load-bearing strands are broken during plastic deformation, the craze can start, but not fully develop. Model predictions are then compared with a series of l...

The Adhesion of Polymers: Relations Between Properties of Polymer Chains and Interface Toughness

A review is presented of the adhesion between polymers with particular emphasis on the processes that occur during failure at the level of polymer chains and how these processes relate to the macroscopic interface toughness. The same processes at the chain level, pull-out and scission, occur in both glassy polymers and elastomers, but the two classes of material are considered separately because their deformation processes around a crack tip are so different. Emphasis is placed on the work in which the author has participated and so the review makes no attempt to be an unbiased survey of the field.

Interdigitation between surface-anchored polymer chains and an elastomer: Consequences for adhesion promotion

We study the adhesion between a crosslinked elastomer and a flat solid surface where polymer chains have been end-grafted. To understand the adhesive feature of such a system, one has to study both the origin of the grafted layer interdigitation with the network, and the end-grafted chains extraction out of the elastomer when it comes unstuck from the solid surface. We shall tackle here the first aspect for which we develop a partial-interdigitation model that lets us analytically predict a critical surface grafting density σ* P1/10N−3/5 beyond which only the thermal fluctuations allow the layer to interdigitate with the elastomer. We then relate this result with recent adhesion measurements.

Electropolymerised acrylic coatings for polymer-metal adhesion enhancement

Electrochemical polymerisation (ECP) of acrylic monomers produces thin coatings on metal substrates and is a potentially useful method for forming adhesion promoting tie-layers at a polymer-metal interface. Uniform, passive films of poly (methyl methacrylate) and poly (glycidyl acrylate) have been formed via a cathodic free radical mechanism on stainless steel electrodes from aqueous electrolytes. The thickness of these films was found to increase with electrolysis time and the passive nature has been demonstrated by cyclic voltammetry studies. Adhesion tests were performed to compare the adhesion strength and failure mechanisms of various adhesives to coated and uncoated stainless steel substrates. The results indicate that ECP tie-layers can significantly increase the adhesive bond strength and alter the failure mechanisms observed. Electropolymerised acrylic coatings on metal substrates are thus seen as a promising approach for pretreatment of metals for adhesion enhancement.

Interactions Between Micron-sized Glass Particles and Poly(dimethyl siloxane) in the Absence and Presence of Applied Load

Abstract A technique using a scanning electron microscope to view a fine particle in contact with a flat substrate whilst under load and during its removal is described. The particle is attached to an atomic force microscope cantilever so that the magnitude of the load can be estimated directly from the imaged deflection. Interactions between 5 to 60 μm spherical glass particles and cross-linked poly(dimethyl siloxane) were studied in the presence and absence of load. WA was estimated to be 74 mJ/m2 from the size of the contact area in the absence of load. Using highly flexible cantilevers to apply load resulted in large shear displacements and forces, which distorted the contact area and assisted in particle removal. These shear effects were eliminated by using a more rigid cantilever to measure a normal pull-off force for which the interface toughness, Gc , exceeded 950 mJ/m2. The large adhesion hysteresis indicated the presence of chemical bonding, presumed to occur between silanol and siloxane groups. The mode of particle detachment varied significantly with the choice of cantilever, showing evidence of both cohesive failure and interfacial crack propagation. The relevance of these results to the interpretation of AFM data is discussed.