A novel self-healing supramolecular polymer system

Utilising supramolecular pi-pi stacking interactions to drive miscibility in two-component polymer blends offers a novel approach to producing materials with unique properties. We report in this paper the preparation of a supramolecular polymer network that exploits this principle. A low molecular weight polydiimide which contains multiple pi-electron-poor receptor sites along its backbone forms homogeneous films with a siloxane polymer that features pi-electron-rich pyrenyl end-groups. Compatibility results from a complexation process that involves chain-folding of the polydiimide to create an optimum binding site for the pi-electron-rich chain ends of the polysiloxane. These complementary pi-electron-rich and -poor receptors exhibit rapid and reversible complexation behaviour in solution, and healable characteristics in the solid state in response to temperature. A mechanism is proposed for this thermoreversible healing behaviour that involves disruption of the intermolecular pi-pi stacking cross-links as the temperature of the supramolecular film is increased. The low T-g siloxane component can then flow and as the temperature of the blend is decreased, pi-pi stacking interactions drive formation of a new network and so lead to good damage-recovery characteristics of the two-component blend.

Preliminary observations on the presence of sustained tendon strain and eccentric contractions of the wrist extensors during a common manual task: implications for lateral epicondylitis

Lateral epicondylitis (LE) is hypothesized to occur as a result of repetitive, strenuous and abnormal postural activities of the elbow and wrist. There is still a lack of understanding of how wrist and forearm positions contribute to this condition during common manual tasks. In this study the wrist kinematics and the wrist extensors’ musculotendon patterns were investigated during a manual task believed to elicit LE symptoms in susceptible subjects. A 42-year-old right-handed male, with no history of LE, performed a repetitive movement involving pushing and turning a spring-loaded mechanism. Motion capture data were acquired for the upper limb and an inverse kinematic and dynamic analysis was subsequently carried out. Results illustrated the presence of eccentric contractions sustained by the extensor carpi radialis longus (ECRL), together with an almost constant level of tendon strain of both extensor carpi radialis brevis (ECRB) and extensor digitorum communis lateral (EDCL) branch. It is believed that these factors may partly contribute to the onset of LE as they are both responsible for the creation of microtears at the tendons’ origins. The methodology of this study can be used to explore muscle actions during movements that might cause or exacerbate LE.

Healing the wounds of war: memories of violence and the making of history in Zimbabwe's most recent past.

How does a society less than two decades after a liberation war which involved large sections of the population come to terms with the memories of violence and war — a war in which there was no clear distinction between insurgent and counter‐insurgent, liberator and oppressor and in which the majority of the casualties can be found among the rural civilian population? This was a predicament not exclusive to Zimbabwe, but one which also applies to Mozambique, South Africa and, more recently, to Rwanda. Since its independence Zimbabwe has been a prime example of successful reconciliation. Ranger has argued that spiritual healing has contributed importantly to coming to terms with the trauma of war through turning violence into history. Here it will be argued that an analysis of the intersections between memories of violence, healing, and history reveals a twofold process. Social healing is made possible by a shift from conviction and compensation to revealing without convicting. At the same time healing provides an arena for communities in which competing and contesting memories of violence are renegotiated. Through these processes sense is being made of the past; history is being made.

Multivalency in healable supramolecular polymers: the effect of supramolecular cross-link density on the mechanical properties and healing of noncovalent polymer networks

Polymers with the ability to heal themselves could provide access to materials with extended lifetimes in a wide range of applications such as surface coatings, automotive components and aerospace composites. Here we describe the synthesis and characterisation of two novel, stimuli-responsive, supramolecular polymer blends based on π-electron-rich pyrenyl residues and π-electron-deficient, chain-folding aromatic diimides that interact through complementary π–π stacking interactions. Different degrees of supramolecular “cross-linking” were achieved by use of divalent or trivalent poly(ethylene glycol)-based polymers featuring pyrenyl end-groups, blended with a known diimide–ether copolymer. The mechanical properties of the resulting polymer blends revealed that higher degrees of supramolecular “cross-link density” yield materials with enhanced mechanical properties, such as increased tensile modulus, modulus of toughness, elasticity and yield point. After a number of break/heal cycles, these materials were found to retain the characteristics of the pristine polymer blend, and this new approach thus offers a simple route to mechanically robust yet healable materials.

A thermoreversible supramolecular polyurethane with excellent healing ability at 45 °C

We report the synthesis and characterization of a healable, elastomeric shape recovery supramolecular polyurethane whose properties result from self-complementary π−π stacking and hydrogen bonding interactions plus phase separation. ESEM analysis and photographic images have revealed that this material can heal at 45 °C in 15 min to recover the mechanical properties of the pristine material with healing efficiencies >99%. This supramolecular polyurethane is also able to recover an applied strain of 25% within 5 min of release of the load.