Sabine Cantournet

Activation and deactivation of self-healing in supramolecular rubbers

A remarkable self-healing property has been achieved recently with rubbers formed by a supramolecular network of oligomers. Here we explore this property through a tack-like experiment where two parts of supramolecular rubber are simply brought into contact and then taken apart. These experiments reveal that the self-adhesive strength of rubber surfaces is significantly enhanced by fracture or other damaging processes. The mechanical energy required to separate two fracture surfaces that were brought back into contact is about one order of magnitude larger than that for surfaces close to thermodynamic equilibrium. Moreover, we find that fracture faces stored apart at room temperature still self-heal after 12 h but that this self-healing can be fully deactivated within a couple of hours by annealing around 90 °C. More generally, these results provide useful quantitative data to investigate the intensity and kinetics of self-healing in these soft rubbers.

Modeling Microdefects Closure Effect with Isotropic/Anisotropic Damage

Continuum damage mechanics (CDM) for metals is often written in terms of an isotropic (scalar) damage. In this case, solutions have been proposed to represent the differences of behavior in tension and in compression also called quasi-unilateral (QU) conditions or microdefects closure effect. A recent anisotropic damage model has been developed to take into account the damage orthotropy induced by plasticity (Lemaitre, J., Demorat R. and Sauzay, M. (2000). Anisotropic Damage Law of Evolution, Eur. J. Mech. A/Solids, 19: 513—524). The purposes here are then two. First, a unified framework for isotropic and anisotropic damage is proposed. Then, it is to extend Ladevèze and Lemaitres framework (Ladevèze, P. and Lemaitre, J. (1984). Damage Effective Stress in Quasi Unilateral Conditions, In: Proceedings of the 16th International Congress of Theoretical and Applied Mechanics, Lyngby, Denmark) for the QU conditions to anisotropic damage induced by plasticity. Yield surfaces and damage versus accumulated plastic strain curves, drawn for different loading, illustrate the effect of the QU conditions on the damage evolution.

A multiscale microstructure model of carbon black distribution in rubber

The increase of observations and computational capabilities favoured the numerical simulation of microstructure to derive the effective properties of materials. Indeed, the multiscale approaches, that use homogenization techniques, enable us to estimate or to give bounds of the overall properties of heterogeneous media. In this work, the objective is to develop a three‐dimensional mathematical model of the morphology of the microstructure of rubber composite containing carbon black nano‐fillers. This multiscale model consists of a combination of some primary models that correspond to the physical scales of the microstructure. It is identified according to an original method that uses statistical moments from experimental transmission electronic microscope (TEM) image data and from numerical TEM simulations. This method leads to three‐dimensional representative simulations of microstructures that take the complex clustering effect of particles in aggregates, into account. Finally, the identified model of the morphology satisfies the experimental percolation rate of the carbon black aggregates in the material.

Hydrogel fibers for ACL prosthesis: Design and mechanical evaluation of PVA and PVA/UHMWPE fiber constructs

Prosthetic devices for anterior cruciate ligament (ACL) reconstruction have been unsuccessful due to mechanical failure or chronic inflammation. Polymer hydrogels combine biocompatibility and unique low friction properties; however, their prior use for ligament reconstruction has been restricted to coatings due to insufficient tensile mechanics. Here, we investigate new constructs of polyvinyl alcohol (PVA) hydrogel fibers. In water, these fibers swell to an equilibrium water content of 50% by weight, retaining a tensile modulus greater than 40 MPa along the fiber axis at low strain. Rope constructs were assembled for ACL replacement and mechanical properties were compared with data from the literature. Pure PVA hydrogel constructs closely reproduce the non-linear tensile stiffness of the native ACL with an ultimate strength of about 2000 N. An additional safety factor in tensile strength was achieved with composite braids by adding ultrahigh molecular weight polyethylene (UHMWPE) fibers around a core of PVA cords. Composition and braiding angle are adjusted to produce a non-linear tensile behavior within the range of the native ligament that can be predicted by a simple rope model. This design was found to sustain over one million cycles between 50 and 450 N with limited damage and less than 20% creep. The promising mechanical performances of these systems provide justification for more extensive in vivo evaluation.

Augmentation of bone tunnel healing in anterior cruciate ligament grafts: application of calcium phosphates and other materials.

Bone tunnel healing is an important consideration after anterior cruciate ligament (ACL) replacement surgery. Recently, a variety of materials have been proposed for improving this healing process, including autologous bone tissue, cells, artificial proteins, and calcium salts. Amongst these materials are calcium phosphates (CaPs), which are known for their biocompatibility and are widely commercially available. As with the majority of the materials investigated, CaPs have been shown to advance the healing of bone tunnel tissue in animal studies. Mechanical testing shows fixation strengths to be improved, particularly by the application of CaP-based cement in the bone tunnel. Significantly, CaP-based cements have been shown to produce improvements comparable to those induced by potentially more complex treatments such as biologics (including fibronectin and chitin) and cultured cells. Further investigation of CaP-based treatment in the bone tunnels during ACL replacement is therefore warranted in order to establish what improvements in healing and resulting clinical benefits may be achieved through its application.

Erasable and reversible wrinkling of halogenated rubber surfaces.

Few surfaces can exist at rest in either wrinkled or unwrinkled states and switch reversibly between these states. Here, we report a new approach to creating reversibly wrinkling systems using the halogenation of rubber to induce a local increase in the glass-transition temperature within a thin layer at the surface. Such systems are obtained by the bromination of molded rubber films. By means of thermomechanical experiments and in situ observations, we show that microscopic wrinkles are produced by unstretching a stretched film below the glass-transition temperature of the brominated layer. These surface patterns are erased within seconds when the wrinkled layer is heated to above its glass transition and recovers its initial equilibrium dimensions. New wrinkles can be produced and erased repeatedly on the same surface. A model is proposed that takes into account the existence of a gradient in bromine content along the thickness of the modified layer. It describes the viscoelastic behavior of these brominated films and captures the temperature dependencies of the thickness of the glassy layer and of the wrinkle wavelength.

Mechanical Testing of a New Prosthetic Anterior Cruciate Ligament Using Biocompatible Fibrous Hydrogel Constructs

The anterior cruciate ligament (ACL) is an important intra-articular structure in the knee joint that prevents excessive anterior tibial translation and resists internal rotational loads. Its rupture is one of the most common injuries of the knee and about 100,000 ACL reconstructions are performed each year in the United States. The current techniques for reconstruction involve replacing the ACL with autografts, most commonly from the hamstrings or patellar tendons, though use of these grafts is associated with various drawbacks, the most prominent of which is donor site morbidity. Over the past 30 years, numerous prosthetic devices for ACL replacement have been made with a wide range of materials. However none of them have demonstrated positive long term results in vivo, and no such devices are currently approved by the FDA for clinical use. Failures of previous devices mostly originate from a lack of biocompatibility due to immunogenic particulation or from mechanical failures causing prosthetic laxity and knee instability as the result of creep or rupture by wear and fatigue.Copyright