On the impact of capillarity for strength at the nanoscale

The interior of nanoscale crystals experiences stress that compensates the capillary forces and that can be large, in the order of 1 GPa. Various studies have speculated on whether and how this surface-induced stress affects the stability and plasticity of small crystals. Yet, experiments have so far failed to discriminate between the surface contribution and other, bulk-related size effects. In order to clarify the issue, we study the variation of the flow stress of a nanomaterial while distinctly different variations of the two capillary parameters surface tension and surface stress are imposed under control of an applied electric potential. Our theory qualifies the suggested impact of $\textit{surface stress}$ as not forceful and instead predicts a significant contribution of the surface energy, as measured by the $\textit{surface tension}$. The predictions for the combined potential- and size dependence of the flow stress are quantitatively supported by the experiment. Previous suggestions, favoring the surface stress as the relevant capillary parameter, are not consistent with the experiment

Anomalous compliance and early yielding of nanoporous gold

We present a study of the elastic and plastic behavior of nanoporous gold in compression, focusing on molecular dynamics simulation and inspecting experimental data for verification. Both approaches agree on an anomalously high elastic compliance in the early stages of deformation, along with a quasi immediate onset of plastic yielding even at the smallest load. Already before the first loading, the material undergoes spontaneous plastic deformation under the action of the capillary forces, requiring no external load. Plastic deformation under compressive load is accompanied by dislocation storage and dislocation interaction, along with strong strain hardening. Dislocation-starvation scenarios are not supported by our results. The stiffness increases during deformation, but never approaches the prediction by the relevant Gibson-Ashby scaling law. Microstructural disorder affects the plastic deformation behavior and surface excess elasticity might modify elastic response, yet we relate the anomalous compliance and the immediate yield onset to an atomistic origin: the large surface-induced prestress induces elastic shear that brings some regions in the material close to the shear instability of the generalized stacking fault energy curve. These regions are elastically highly compliant and plastically weak

Oxygen persufflation as adjunct in liver preservation (OPAL): Study protocol for a randomized controlled trial

<p>Abstract</p> <p>Background</p> <p>Early graft dysfunction due to preservation/reperfusion injury represents a dramatic event after liver transplantation. Enhancement of donor organ criteria, in order to cope with the ever increasing donor shortage, further increases graft susceptibility to ischemic alterations.</p> <p>Major parts of post-preservation injury, however, occur at the time of warm reperfusion but not during ischemic storage; successful reperfusion of ischemic tissue in turn depends on an adequate redox and intracellular signal homeostasis. The latter has been shown experimentally to be favorably influenced by oxygen persufflation within short time spans. Thus viability of marginally preserved liver grafts could still be augmented by transient hypothermic reconditioning <b><it>even after </it></b>normal procurement and static cold storage. The present study is aimed to confirm the conceptual expectations, that hypothermic reconditioning by gaseous oxygen persufflation is a useful method to suppress injurious cellular activation cascades and to improve post-ischemic recovery of marginally preserved liver grafts.</p> <p>Methods/Design</p> <p>OPAL is a prospective single center randomized proof of concept study, including two parallel groups in a total of 116 liver transplant patients. The effect of an in hospital treatment of the isolated liver graft by 2 hours of oxygen persufflation immediately prior to transplantation will be assesses as compared to standard procedure (cold storage without further intervention). The primary endpoint is the peak transaminase serum level (AST) during the first three days after transplantation as a surrogate readout for parenchymal liver injury. Other outcomes comprise patient and graft survival, time of intensive care requirement, hepatic tissue perfusion 1h after revascularisation, early onset of graft dysfunction based on coagulation parameters, as well as the use of a refined scoring-system for initial graft function based on a multi-parameter (AST, ALT, Quick and bilirubin) score. Furthermore, the effect of OPAL on molecular pathways of autophagy and inflammatory cell activation will be evaluated. Final analysis will be based on all participants as randomized (intention to treat).</p> <p>Trial Registration</p> <p>Current Controlled Trials <a href="http://www.controlled-trials.com/ISRCTN00167887">ISRCTN00167887</a></p

Synthesis of uniform bulk nanoporous palladium with tunable structure

This work presents systematic investigations on the synthesis of hierarchical nanoporous Pd via electrochemical dealloying of CuPd alloys in sulfuric acid. The impact of electrode potential, dealloying temperature, and additional annealing on microstructure and morphology is explored. Dealloying Cu85Pd15 in 1M sulfuric acid at elevated temperature provides a facile strategy to produce bulk nanoporous Pd samples which are uniform, hierarchically nanoporous, and free of macro-scale cracks. The question “Why will one-step template-free dealloying yield a hierarchical and not unimodal nanoporous structure?” is discussed. The impact of passivation and of a percolating Cu-rich cluster on the pore structure is inspected. A structural instability concept for dealloying of dilute master alloys is preferred as the underlying mechanism. Nanoporous Pd with classical, unimodal pore structure and tunable ligament size ranging from 80 to 270 nm emerges when the as-prepared hierarchical nanoporous Pd is annealed. The material of this study may provide a model system that complements nanoporous Au for studies of bulk nanoscale metal networks as functional and structural materials

Dealloying-based interpenetrating-phase nanocomposites matching the elastic behavior of human bone

The long-term performance of orthopedic implants depends crucially on a close match between the mechanical behavior of bone and of the implant material. Yet, the present man-made materials with the required biocompatibility and strength are substantially stiffer than bone. This mismatch results in stress shielding, which can lead to the loss of bone mass and may even lead to a revision surgery. Here we report a new materials design strategy towards metal-polymer composites that are based on constituents with established biocompatibility and that can be matched to bone. Ti-based nanoporous alloys, prepared by liquid-metal dealloying, are infiltrated with epoxy to form interpenetrating-phase nanocomposites. At up to 260 MPa, their yield strength is technologically interesting for a deformable light-weight material. More importantly, Young's modulus can be adjusted between 4.4 and 24 GPa, which affords matching to bone. As another parallel to bone, the strength of the composite materials is strain-rate dependent. These findings suggest that the novel composite materials may provide the basis for promising future implant materials

Verifying Larché-Cahn elasticity, a milestone of 20th-century thermodynamics

Many materials phenomena are governed by the interaction between chemistry and mechanics. However, it was only in the second half of the 20th century that the theory of open system elasticity by Francis Larché and John W. Cahn concatenated the fields of solid mechanics and alloy chemistry. As the theory's central materials descriptors, the open system elastic parameters describe how solids deform under stress when solute can rearrange at equilibrium while the chemical potential is held constant. Here, we report experiments verifying the predictions for these parameters. We study the elasticity of nanoporous Pd-H and Pd-Au-H during load cycles imposed by a dynamic mechanical analyzer. Short diffusion paths afford fast equilibration of H in the local strain gradients that carry the macroscopic elastic deformation. The experiment is in excellent agreement with the theory, confirming a central prediction of one of the key contributions to 20th-century thermodynamics

Electro-chemo-mechanical coupling of nanoporous gold at the microscale

The observation of reversible strengthening and stiffening of nanoporous gold (NPG) under electrochemical potential has opened opportunities to exploit this material for multifunctional applications. Yet the complex structural geometry and length-scales involved make a definitive understanding of structural correlations to the behaviors difficult at best. Achievement of coupled electro-chemo-mechanical testing at the micrometer scale is a key step toward this goal. Here, we introduce an experimental approach to investigate the elastic and plastic behaviors of NPG under electrochemical potential at the microscale using a modified nanoindentation setup and multiple load function. The in situ experiments in electrolyte show a significant increase by 32% in strength of pillars in a positive potential regime where oxygen adsorption occurred. This response was found to be reversible, which agrees with macroscopic results, while the elastic modulus was shown to be insensitive to the applied potential - an observation inconsistent with recent bulk dynamic mechanical analysis results

On the consequences of intrinsic and extrinsic size effects on the mechanical response of nanoporous Au

In this study, the consequence of intrinsic and extrinsic size effects on mechanical responses of nanoporous gold is investigated via microcompression testing. By varying the micropillar diameter (D) between 1 µm and 20 µm and the ligament size (L), 50 nm and 350 nm, a critical ratio (α = D/L = 20) was found, above which the test structure can be considered a representative volume element, resulting in identical mechanical response and uniform deformation. Below that value, both flow stress and elastic modulus decrease with decreasing pillar diameter, as evidenced for a measurement series with a fixed ligament size of 350 nm where the flow stress decreased by more than 50% (from approximately 5 to 2.5 MPa) and the elastic modulus was reduced from approximately 0.5 GPa to almost zero. Stochastic behavior along with non-uniform deformation and failure is observed for α < 10, suggesting that the size of the load-bearing units in this material is about 10 times the corresponding ligament size

Nanoporous gold : testing macro-scale samples to probe small-scale mechanical behavior

Nanoporous gold made by dealloying exemplifies how the exciting mechanical properties of nanoscale objects can be exploited in designing materials from which macroscopic things can be formed. The homogeneous microstructure and the possibility of adjusting the ligament size, L, between few and few hundred nm, along with the high deformability and reproducible mechanical behavior predestine the material for model studies of small-scale plasticity using reliable macroscopic testing schemes on mm- or cm-size samples. Such experiments tend to agree with the Gibson-Ashby scaling relation for strength versus solid fraction, while suggesting an essentially L−1 scaling of the local strength of the ligaments. By contrast, the elastic compliance is dramatically enhanced compared to the Gibson-Ashby relation for the stiffness. Contrary to intuition, the anomalously compliant behavior of the nanomaterial goes along with a trend for more stiffness at smaller L. This article discusses surface excess elasticity, nonlinear elastic behavior and specifically shear instability of the bulk, network connectivity, and the surface chemistry as relevant issues which deserve further study