Hybrid hydrogels for load-bearing implants

Load-bearing tissues such as articular cartilage or meniscus are not infallible. They might fail due to trauma, over-solicitations, or diseases, which could subsequently alter the mobility of the patient. Repairing these damaged tissues in a minimally invasive way is nowadays widely studied.

Hydrogels are promising for repairing soft tissues. However, trying to reproduce the highly hierarchical microstructures of load-bearing tissues is extremely complicated. In fact, conceiving hydrogels with optimal properties for specific applications is challenging as most of the hydrogel's properties are interrelated, such as toughness, stiffness, swelling, or deformability. The improvement of one property usually comes at the cost of another.

This thesis aims to develop different hydrogel microstructures and evaluate their potential for load-bearing implants. In particular, the study focuses on (i) designing tough and fatigue resistant hydrogels, (ii) establishing a methodology to control the stiffness and the swelling of hydrogels independently, and (iii) considering processing ease by tailoring each hydrogel precursor viscosity.

An extensive parametric study on hydrogels' structure and composition allowed establishing complete property charts for mechanical, swelling, and rheological properties. Seven different hydrogel structures based on poly(ethylene glycol) dimethacrylate were developed: neat, double network, composite, double network composite, granular, hybrid granular, and silk granular hydrogels. The precursors of neat hydrogels had the lowest viscosity. Microgels of similar composition were added to the precursor to adapt and increase its viscosity for unconfined applications. In parallel, adding nano-fibrillated cellulose fibers was effective for increasing toughness. This method was more efficient than creating a double network with alginate. Moreover, fatigue tests revealed that hydrogel composites successfully survive 10 million loading cycles at 20% applied strain. However, it became softer after the first loading cycles and behaved similarly to the Mullins effect. Subsequently, we assessed how cyclic loading affects fracture behavior, distribution of strain fields, and microstructure. The study demonstrated that cyclic loading on hydrogel composites re-arrange the fiber network without seriously deteriorating the mechanical properties. Additionally, we demonstrated that combining composite and microgel approaches, i.e. hybrid granular hydrogels, effectively tailored hydrogels' swelling and viscosity without significantly affecting stiffness, toughness, and deformability. Finally, the microgels were swollen in silk fibroin solution for forming self-reinforced silk granular hydrogels. Those hydrogels exhibited considerably higher stiffness and lower swelling but also reduced elongation performances.

We demonstrated that hydrogels' mechanical and physical properties could be effectively controlled with the microstructures and compositions of well-known biomaterials. Subsequently, a hydrogel composite and a silk granular hydrogel, based this time on gelatin hydrogels, were synthesized, validating the potential of studied structures with other hydrogels and microgels. Finally, the analyzed material systems can be combined through a sequential layering, forming hybrid hydrogels, to obtain local or gradient properties addressing specific biomedical applications, soft robotics, sensing applications, or even food packaging.

Fracture and Fatigue of Adhesively-Bonded Fiber-Reinforced Polymer Structural Joints

Ye Zhang

Being good structural replacement for other conventional material, the pultruded glass fiber reinforced polymer (GFRP) profiles are being increasingly used in civil engineering structures. The connection between components is considered the most suspect area for failure initiation. The adhesive bonding is preferred for FRP composite structures, rather than the mechanical fastening, due to the brittle failure nature of composite materials. During past decades, many efforts have been made by researchers to better understand the mechanism of adhesive bonding, to analyze the stress distributions and to improve the strength of composite structural joints. However there is still no commonly accepted design code/standard existing for adhesively-bonded joints in civil engineering infrastructures since several important knowledge gaps are to be filled. Besides the joint strength at failure, the characterization and modeling of the progressive failure process, in particular involving the so-called crack initiation and propagation phases, is also an important concern. By employing the strain energy release rate (SERR) as the fracture parameter, the linear-elastic fracture mechanics (LEFM) approach is considered an efficient method to model the fracture behavior of structural joints. However, due to the uncontrollable crack initiation and the complex geometric configurations, the crack measurement techniques and the calculation method for the SERR are to be validated. In fracture mechanics, the fracture of a material or component can be described by a single mode or the combinations of the following three basic modes: opening mode (Mode I), shearing mode (Mode II), and tearing mode (Mode III). During the fracture of a structural joint, crack initiation and propagation are driven by combined through-thickness tensile (peeling), and shear stresses, thus resulting in a mixed mode fracture. In order to use the fracture results of structural joints to form the mixed fracture criterion for a specific composite material, a feasible analytical or numerical method are to be developed to determine the Mode I and II components of the SERR during fracture. Although many efforts have been made to better understand the short-term behavior of structural joint under quasi-static loading, the long-term performance under fatigue loading and different environmental conditions is a more demanding task when adhesively-bonded joints are applied in a real structure. Most of structural failures occur due to mechanisms that are driven by fatigue loading and for composite structures, the fatigue produced by the repeated application of live load is more critical due to its lighter self-weight, in other words the lower dead load. Besides the fatigue loading, a structure in practice may also experience the combined environmental effects of two basic factors: temperature and humidity. These environmental conditions may directly affect properties of structural joints, including the failure mechanism, the stiffness and strength, the crack initiation and propagation and etc.. Thus, the missing knowledge and confidences in the long-term behavior under cyclic loading and the durability under different environmental conditions are the main obstacles to the further development of FRP composites in civil engineering infrastructures. In this research, the mechanical and fracture behavior of adhesively-bonded double-lap and stepped-lap joints (DLJs and SLJs) composed of pultruded GFRP laminates and an epoxy adhesive were experimentally and numerically investigated under both quasi-static and fatigue loadings. The crack measurement techniques and the calculation methods for the SERR were validated for DLJs and SLJs. The LEFM approach was successfully applied to characterize and model the progressive failure process of structural joints. The Mode I and II components of the SERR of DLJs and SLJs were determined using the Virtual Crack Closure Technique in finite element analysis. Combining with the results of pure Mode I and II experiments, a mixed mode fracture criterion for pultruded GFRP composite was formed. Under fatigue loading, the fatigue behavior of structural joints was successfully modeled by using the stiffness-based and fracture mechanics approaches, besides the F-N curves. Based on the stiffness degradation, a linear and a sigmoid non-linear model were established and the fatigue live corresponding to the failure and allowable stiffness degradation can be predicted. Concerning fracture mechanics approach, the Fatigue Crack Growth (FCG) curves were formed for DLJs and SLJs and the corresponding fracture parameters were obtained. Similarly to stiffness-based approach, fatigue lives corresponding to the failure and allowable crack length can be predicted. The environmental effects on both short- and long-term performances of structural joints were experimentally evaluated and numerically modeled based on experimental results. The temperature-dependent joint stiffness can be predicted using the finite element analysis based on the thermomechanical properties of constituent materials. A relationship between the equivalent quasi-static joint strength under different environmental conditions and the cyclic stresses and the fatigue life was established.

EPFL2010

Shear Thickening Fluid Impregnated Foam Composites for Vibration Control and Impact Protection

Mathieu Soutrenon

Highly concentrated suspensions of silica particles present shear thickening properties, shifting from a low to a high viscosity state, instantly and reversibly at a critical shear rate. Their viscosity increases by up to 3 orders of magnitude, changing from a honey-like liquid to a brittle solid material. This sharp rise in viscosity is associated with a large absorption of energy that can be used in damping applications. These shear thickening fluids (STF) are among the few passive materials that can simultaneously bring both an increase in damping and in stiffness properties. In mechanical design, this leads potentially to a weight reduction of the overall system. This thesis work is aimed to develop and test a composite material solution for vibration control and impact protection, using STF as the damping element. A main challenge was to overcome the fact that STF are liquid at rest, and very sensitive to their environment. The proposed damping material was therefore constituted of foam impregnated with STF and encapsulated with silicone (STF/foam). A comparison of properties with other damping materials such as Smactane®was emphasized along the thesis. Storage and processing conditions of STF constituted of highly concentrated suspensions were shown to affect their rheological properties similarly to other sensitive parameters such as particle concentration. Rigorous processing methods were thus required to produce STF with defined and stable rheological properties. The use of sonication was preferred to disperse the aggregates of particles in concentrated colloidal suspensions due to the packing of the dry powder. Contact with air or humidity deteriorates the shear thickening properties of STF. Storage of STF in a freezer at −24 ◦C or under nitrogen prevents this. The use of a physical barrier to air and humidity such as silicone to protect STF is also shown to greatly reduce the ageing problem. The energy dissipated during a cyclic strain cycle was used as a measure of the damping property of the STF, and compared to that of other materials. It was measured with dynamic rheological measurements performed on suspensions with variations of particle concentration, size and test frequency. STF were shown to dissipate a large amount of energy during their transition, which increases with the increase of frequency and particle concentration and decrease with the increase of particle size. In specific cases of large strain amplitude, they potentially dissipate more energy than viscoelastic materials such as rubber. An open cell melamine resin foam was used as a lightweight scaffold to provide a three dimensional structure to the STF. The foam distributes the load and locally shears the STF. The shape of the foam is easily adjustable. To impregnate the foam with the STF, a system similar to vacuum infusion was used. The foam was placed under vacuum in a mold and the STF heated at 70 ◦C to reduce its viscosity and shear thickening properties was sucked in the foam with the depressurization. The STF/foam systems were then encapsulated in silicone to protect the STF/foam damping pads from contamination and avoid outgassing. During compression tests at low frequencies and large deformations, we demonstrated that STF could be activated in this type of structure, with mechanical properties comparable to those of a viscous honey-like fluid at rest and silicone when the STF is in the solid state. The same behavior was observed during impact solicitations. STF/foam presents a very low coefficient of restitution and absorbs the shock wave associated with impacts. Shock tests done separately confirm the shock absorption properties of STF/foam even if the STF is not activated. The combination of mechanical and damping properties of the foam/STF systems remain lower than for very high performance damping materials like Smactane®. The reasons are their low mechanical compression and shear properties at rest and the need to overcome a threshold strain or stress to activate the STF. However, the large dissimilarity between the states before and after the transition makes these materials interesting for impact or large strain amplitude applications such as sole for running shoes or several space structures.