Laurent Corté

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.

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.

Poly(vinyl alcohol) hydrogel coatings with tunable surface exposure of hydroxyapatite

Insufficient bone anchoring is a major limitation of artificial substitutes for connective osteoarticular tissues. The use of coatings containing osseoconductive ceramic particles is one of the actively explored strategies to improve osseointegration and strengthen the bone-implant interface for general tissue engineering. Our hypothesis is that hydroxyapatite (HA) particles can be coated robustly on specific assemblies of PVA hydrogel fibers for the potential anchoring of ligament replacements. A simple dip-coating method is described to produce composite coatings made of microscopic hydroxyapatite (HA) particles dispersed in a poly(vinyl alcohol) (PVA) matrix. The materials are compatible with the requirements for implant Good Manufacturing Practices. They are applied to coat bundles of PVA hydrogel fibers used for the development of ligament implants. By means of optical and electronic microscopy, we show that the coating thickness and surface state can be adjusted by varying the composition of the dipping solution. Quantitative analysis based on backscattered electron microscopy show that the exposure of HA at the coating surface can be tuned from 0 to over 55% by decreasing the weight ratio of PVA over HA from 0.4 to 0.1. Abrasion experiments simulating bone-implant contact illustrate how the coating cohesion and wear resistance increase by increasing the content of PVA relative to HA. Using pullout experiments, we find that these coatings adhere well to the fiber bundles and detach by propagation of a crack inside the coating. These results provide a guide to select coated implants for anchoring artificial ligaments.

Mechanical Study of Novel VPS-Titanium Coating on Polyethylene Substrates

Thick metallic or ceramic functional coatings onto polymers are of great interest for different domains such as the aerospace and medical industries. A vacuum plasma spray process has been developed to produce coatings on high- and low-temperature melting polymers including PEEK and polyethylene. This study reports the first experimental characterization of the strength and adherence of such titanium coatings on medical grade polyethylene substrates. Four-point bending coupled to microscopic observations show the existence of a critical tensile strain of 1% corresponding to the onset of cracking in the coating. For strains up to 6%, the crack density increases without any noticeable debonding. Fatigue tests over 106 cycles reveal that under this critical strain the coating remains uncracked while above it, the cracks number and size remain stable with no noticeable coating detachment. A protocol for laser shock adhesion testing (LASAT®) was developed to characterize the coating-substrate adhesion and captured the existence of a debonding threshold. These results provide quantitative guides for the design of orthopedic implants for which such a titanium coating is used to enhance anchorage to bone tissues. More generally, they open the way for systematic measurements quantifying the adhesion of metallic coating onto polymer substrates.

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