Lower hardness than strength: The auxetic composite microstructure of limpet tooth.

The limpet tooth is widely recognized as nature's strongest material, with reported strength values up to 6.5 GPa. Recently, microscale auxeticity has been discovered in the leading part of the tooth, providing a possible explanation for this extreme strength. Utilizing micromechanical experiments, we find hardness values in nanoindentation that are lower than the respective strength observed in micropillar compression tests. Using micromechanical modeling, we show that this unique behavior is a result of local tensile strains during indentation, originating from the microscale auxeticity. As the limpet tooth lacks ductility, these tensile strains lead to microdamage in the auxetic regions of the microstructure. Consequently, indentation with a sharp indenter always probes a damaged version of the material, explaining the lower hardness and modulus values gained from nanoindentation. Micropillar tests were found to be mostly insensitive to such microdamage due to the lower applied strain and are therefore the suggested method for characterizing auxetic nanocomposites. STATEMENT OF SIGNIFICANCE: This work explores the micromechanical properties of limpet teeth, nature's strongest biomaterial, using micropillar compression testing and nanoindentation. The limpet tooth microstructure consists of ceramic nanorods embedded in a matrix of amorphous SiO2 and arranged in a pattern that leads to local auxetic behavior. We report lower values for nanoindentation hardness than for compressive strength, a unique behavior usually not achievable in conventional materials. Utilizing micromechanical finite element simulations, we identify the reason for this behavior to be microdamage formation resultant of the auxetic behavior, sharp indenter tip and lack of ductility of the limpet tooth microstructure. This formation of microdamage is not expected in micropillar compression tests due to lower locally imposed strain.

Special Issue "Novel Structural and Functional Material Properties Enabled by Nanocomposite Design".

Nanocomposites bear the potential to enable novel material properties that considerably exceed the capabilities of their individual constituent phases, thereby enabling the exploration of white areas on material property charts [...].

Limpet teeth microstructure unites auxeticity with extreme strength and high stiffness.

Materials displaying negative Poisson's ratio, referred to as auxeticity, have been found in nature and created in engineering through various structural mechanisms. However, uniting auxeticity with high strength and high stiffness has been challenging. Here, combining in situ nanomechanical testing with microstructure-based modeling, we show that the leading part of limpet teeth successfully achieves this combination of properties through a unique microstructure consisting of an amorphous hydrated silica matrix embedded with bundles of single-crystal iron oxide hydroxide nanorods arranged in a pseudo-cholesteric pattern. During deformation, this microstructure allows local coordinated displacement and rotation of the nanorods, enabling auxetic behavior while maintaining one of the highest strengths among natural materials. These findings lay a foundation for designing biomimetic auxetic materials with extreme strength and high stiffness.

100 years after Griffith: From brittle bulk fracture to failure in 2D materials.

Brittle fracture and ductile failure are critical events for any structural or functional component, as it marks the end of lifetime and potential hazard to human life. As such, materials scientists continuously strive to better understand and subsequently avoid these events in modern materials. A century after the seminal initial contribution by Griffith, fracture mechanics has come a long way and is still experiencing vivid progress. Building on classical fracture testing standards, advanced in situ fracture experiments allow local quantitative probing of fracture processes on different length scales, while microscopic analysis grants access to chemical and structural information along fracture paths in previously unseen detail. This article will provide an overview of how these modern developments enhance our understanding of local fracture processes and highlight future trends toward designing strong yet ductile and damage-tolerant materials.

A Perspective to Control Laser-Induced Periodic Surface Structure Formation at Glancing-Incident Femtosecond Laser-Processed Surfaces.

The favorable combination of high material removal rate and low influence on the material beneath the ultra-short pulsed laser-processed surface are of particular advantage for sample preparation. This is especially true at the micrometer scale or for the pre-preparation for a subsequent focused ion beam milling process. Specific surface features, the laser-induced periodic surface structures, are generated on femtosecond laser-irradiated surfaces in most cases, which pose an issue for surface-sensitive mechanical testing or microstructural investigations. This work strives for an approach to enhance the surface quality of glancing-incident laser-processed surfaces on the model material copper with two distinctly different grain sizes. A new generalized perspective is presented, in which optimized parameter selection serves to counteract the formation of the laser-induced periodic surface structures, enabling, for example, grain orientation mapping directly on femtosecond laser processed surfaces. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s11837-021-04963-w.

High-Temperature Nanoindentation of an Advanced Nano-Crystalline W/Cu Composite.

The applicability of nano-crystalline W/Cu composites is governed by their mechanical properties and microstructural stability at high temperatures. Therefore, mechanical and structural investigations of a high-pressure torsion deformed W/Cu nanocomposite were performed up to a temperature of 600 °C. Furthermore, the material was annealed at several temperatures for 1 h within a high-vacuum furnace to determine microstructural changes and surface effects. No significant increase of grain size, but distinct evaporation of the Cu phase accompanied by Cu pool and faceted Cu particle formation could be identified on the specimen's surface. Additionally, high-temperature nanoindentation and strain rate jump tests were performed to investigate the materials mechanical response at elevated temperatures. Hardness and Young's modulus decrease were noteworthy due to temperature-induced effects and slight grain growth. The strain rate sensitivity in dependent of the temperature remained constant for the investigated W/Cu composite material. Also, the activation volume of the nano-crystalline composite increased with temperature and behaved similar to coarse-grained W. The current study extends the understanding of the high-temperature behavior of nano-crystalline W/Cu composites within vacuum environments such as future fusion reactors.

Addressing H-Material Interaction in Fast Diffusion Materials-A Feasibility Study on a Complex Phase Steel.

Hydrogen embrittlement (HE) is one of the main limitations in the use of advanced high-strength steels in the automotive industry. To have a better understanding of the interaction between hydrogen (H) and a complex phase steel, an in-situ method with plasma charging was applied in order to provide continuous H supply during mechanical testing in order to avoid H outgassing. For such fast-H diffusion materials, only direct observation during in-situ charging allows for addressing H effects on materials. Different plasma charging conditions were analysed, yet there was not a pronounced effect on the mechanical properties. The H concentration was calculated while using a simple analytical model as well as a simulation approach, resulting in consistent low H values, below the critical concentration to produce embrittlement. However, the dimple size decreased in the presence of H and, with increasing charging time, the crack propagation rate increased. The rate dependence of flow properties of the material was also investigated, proving that the material has no strain rate sensitivity, which confirmed that the crack propagation rate increased due to H effects. Even though the H concentration was low in the experiments that are presented here, different technological alternatives can be implemented in order to increase the maximum solute concentration.

In-situ observation of the initiation of plasticity by nucleation of prismatic dislocation loops.

The elastic-to-plastic transition during the deformation of a dislocation-free nanoscale volume is accompanied by displacement bursts associated with dislocation nucleation. The dislocations that nucleate during the so-called "pop-in" burst take the form of prismatic dislocation loops (PDLs) and exhibit characteristic burst-like emission and plastic recovery. Here, we report the in-situ transmission electron microscopy (TEM) observation of the initial plasticity ensued by burst-like emission of PDLs on nanoindentation of dislocation-free Au nanowires. The in-situ TEM nanoindentation showed that the nucleation and subsequent cross slip of shear loop(s) are the rate-limiting steps. As the indentation size increases, the cross slip of shear loop becomes favored, resulting in a transition from PDLs to open half-loops to helical dislocations. In the present case of nanoindentation of dislocation-free volumes, the PDLs glide out of the indentation stress field while spreading the plastic zone, as opposed to the underlying assumption of the Nix-Gao model.

Bioinspired nacre-like alumina with a bulk-metallic glass-forming alloy as a compliant phase.

Bioinspired ceramics with micron-scale ceramic "bricks" bonded by a metallic "mortar" are projected to result in higher strength and toughness ceramics, but their processing is challenging as metals do not typically wet ceramics. To resolve this issue, we made alumina structures using rapid pressureless infiltration of a zirconium-based bulk-metallic glass mortar that reactively wets the surface of freeze-cast alumina preforms. The mechanical properties of the resulting Al2O3 with a glass-forming compliant-phase change with infiltration temperature and ceramic content, leading to a trade-off between flexural strength (varying from 89 to 800 MPa) and fracture toughness (varying from 4 to more than 9 MPa·m½). The high toughness levels are attributed to brick pull-out and crack deflection along the ceramic/metal interfaces. Since these mechanisms are enabled by interfacial failure rather than failure within the metallic mortar, the potential for optimizing these bioinspired materials for damage tolerance has still not been fully realized.

High Temperature Flow Behavior of Ultra-Strong Nanoporous Au assessed by Spherical Nanoindentation.

Nanoporous metals have attracted attention in various research fields in the past years since their unique microstructures make them favorable for catalytic, sensory or microelectronic applications. Moreover, the refinement of the ligaments down to the nanoscale leads to an exceptionally high strength. To guarantee a smooth implementation of nanoporous metals into modern devices their thermo-mechanical behavior must be properly understood. Within this study the mechanical flow properties of nanoporous Au were investigated at elevated temperatures up to 300 °C. In contrast to the conventional synthesis by dealloying of AuAg precursors, the present foam was fabricated via severe plastic deformation of an AuFe nanocomposite and subsequent selective etching of iron, resulting in Au ligaments consisting of nanocrystalline grains, while remaining Fe impurities excessively stabilize the microstructure. A recently developed spherical nanoindentation protocol was used to extract the stress-strain curves of nanoporous Au. A tremendous increase of yield strength due to ligament and grain refinement was observed, which is largely maintained at high temperatures. Reviewing literature will evidence that the combined nanocrystalline and nanoporous structure leads to remarkable mechanical properties. Furthermore, comparison to a previous Berkovich nanoindentation study outlines the conformity of different indentation techniques.

Substrate-Influenced Thermo-Mechanical Fatigue of Copper Metallizations: Limits of Stoney's Equation.

Rapid progress in the reduction of substrate thickness for silicon-based microelectronics leads to a significant reduction of the device bending stiffness and the need to address its implication for the thermo-mechanical fatigue behavior of metallization layers. Results on 5 µm thick Cu films reveal a strong substrate thickness-dependent microstructural evolution. Substrates with hs = 323 and 220 µm showed that the Cu microstructure exhibits accelerated grain growth and surface roughening. Moreover, curvature-strain data indicates that Stoney's simplified curvature-stress relation is not valid for thin substrates with regard to the expected strains, but can be addressed using more sophisticated plate bending theories.

The effect of size on the strength of FCC metals at elevated temperatures: annealed copper.

As the length scale of sample dimensions is reduced to the micron and sub-micron scales, the strength of various materials has been observed to increase with decreasing size, a fact commonly referred to as the 'sample size effect'. In this work, the influence of temperature on the sample size effect in copper is investigated using in situ microcompression testing at 25, 200 and 400 °C in the SEM on vacuum-annealed copper structures, and the resulting deformed structures were analysed using X-ray µLaue diffraction and scanning electron microscopy. For pillars with sizes between 0.4 and 4 µm, the size effect was measured to be constant with temperature, within the measurement precision, up to half of the melting point of copper. It is expected that the size effect will remain constant with temperature until diffusion-controlled dislocation motion becomes significant at higher temperatures and/or lower strain rates. Furthermore, the annealing treatment of the copper micropillars produced structures which yielded at stresses three times greater than their un-annealed, FIB-machined counterparts.

Synthesis and Mechanical Characterisation of an Ultra-Fine Grained Ti-Mg Composite.

The importance of lightweight materials such as titanium and magnesium in various technical applications, for example aerospace, medical implants and lightweight construction is well appreciated. The present study is an attempt to combine and improve the mechanical properties of these two materials by forming an ultra-fine grained composite. The material, with a composition of 75 vol% (88.4 wt%) Ti and 25 vol% (11.4 wt%) Mg , was synthesized by powder compression and subsequently deformed by high-pressure torsion. Using focused ion beam machining, miniaturised compression samples were prepared and tested in-situ in a scanning electron microscope to gain insights into local deformation behaviour and mechanical properties of the nanocomposite. Results show outstanding yield strength of around 1250 MPa, which is roughly 200 to 500 MPa higher than literature reports of similar materials. The failure mode of the samples is accounted for by cracking along the phase boundaries.

Thermally Activated Deformation Behavior of ufg-Au: Environmental Issues During Long-Term and High-Temperature Nanoindentation Testing.

For testing time-dependent material properties by nanoindentation, in particular for long-term creep or relaxation experiments, thermal drift influences on the displacement signal are of prime concern. To address this at room and elevated temperatures, we tested fused quartz at various contact depths at room temperature and ultra-fine grained (ufg) Au at various temperatures. We found that the raw data for fused quartz are strongly affected by thermal drift, but corrected by use of dynamic stiffness measurements all the datasets collapse. The situation for the ufg Au shows again that the data are only useful with drift correction, but with this applied it turns out that there is a significant change of elastic and plastic properties when exceeding 200°C, which is also reflected by an increasing strain rate sensitivity.

Fabrication and thermo-mechanical behavior of ultra-fine porous copper.

Porous materials with ligament sizes in the submicrometer to nanometer regime have a high potential for future applications such as catalysts, actuators, or radiation tolerant materials, which require properties like high strength-to-weight ratio, high surface-to-volume ratio, or large interface density as for radiation tolerance. The objective of this work was to manufacture ultra-fine porous copper, to determine the thermo-mechanical properties, and to elucidate the deformation behavior at room as well as elevated temperatures via nanoindentation. The experimental approach for manufacturing the foam structures used high pressure torsion, subsequent heat treatments, and selective dissolution. Nanoindentation at different temperatures was successfully conducted on the ultra-fine porous copper, showing a room temperature hardness of 220 MPa. During high temperature experiments, oxidation of the copper occurred due to the high surface area. A model, taking into account the mechanical properties of the copper oxides formed during the test, to describe the measured mechanical properties in dependence on the proceeding oxidation was developed. The strain rate sensitivity of the copper foam at room temperature was ∼0.03 and strongly correlated with the strain rate sensitivity of ultra-fine grained bulk copper. Although oxidation occurred near the surface, the rate-controlling process was still the deformation of the underlying copper. An increase in the strain rate sensitivity was observed, comparably to that of ultra-fine-grained copper, which can be linked to thermally activated processes at grain boundaries. Important insights into the effects of oxidation on the deformation behavior were obtained by assessing the activation volume. Oxidation of the ultra-fine porous copper foam, thereby hindering dislocations to exit to the surface, resulted in a pronounced reduction of the apparent activation volume from ~800 to ~50 b3, as also typical for ultra-fine grained materials.

Analysis of the population structure of Anaplasma phagocytophilum using multilocus sequence typing.

Anaplasma phagocytophilum is a Gram-negative obligate intracellular bacterium that replicates in neutrophils. It is transmitted via tick-bite and causes febrile disease in humans and animals. Human granulocytic anaplasmosis is regarded as an emerging infectious disease in North America, Europe and Asia. However, although increasingly detected, it is still rare in Europe. Clinically apparent A. phagocytophilum infections in animals are mainly found in horses, dogs, cats, sheep and cattle. Evidence from cross-infection experiments that A. phagocytophilum isolates of distinct host origin are not uniformly infectious for heterologous hosts has led to several approaches of molecular strain characterization. Unfortunately, the results of these studies are not always easily comparable, because different gene regions and fragment lengths were investigated. Multilocus sequence typing is a widely accepted method for molecular characterization of bacteria. We here provide for the first time a universal typing method that is easily transferable between different laboratories. We validated our approach on an unprecedented large data set of almost 400 A. phagocytophilum strains from humans and animals mostly from Europe. The typability was 74% (284/383). One major clonal complex containing 177 strains was detected. However, 54% (49/90) of the sequence types were not part of a clonal complex indicating that the population structure of A. phagocytophilum is probably semiclonal. All strains from humans, dogs and horses from Europe belonged to the same clonal complex. As canine and equine granulocytic anaplasmosis occurs frequently in Europe, human granulocytic anaplasmosis is likely to be underdiagnosed in Europe. Further, wild boars and hedgehogs may serve as reservoir hosts of the disease in humans and domestic animals in Europe, because their strains belonged to the same clonal complex. In contrast, as they were only distantly related, roe deer, voles and shrews are unlikely to harbor A. phagocytophilum strains infectious for humans, domestic or farm animals.

Reversible cyclic deformation mechanism of gold nanowires by twinning-detwinning transition evidenced from in situ TEM.

Mechanical response of metal nanowires has recently attracted a lot of interest due to their ultra-high strengths and unique deformation behaviours. Atomistic simulations have predicted that face-centered cubic metal nanowires deform in different modes depending on the orientation between wire axis and loading direction. Here we report, by combination of in situ transmission electron microscopy and molecular dynamic simulation, the conditions under which particular deformation mechanisms take place during the uniaxial loading of [110]-oriented Au nanowires. Furthermore, by performing cyclic uniaxial loading, we show reversible plastic deformation by twinning and consecutive detwinning in tension and compression, respectively. Molecular dynamics simulations rationalize the observed behaviours in terms of the orientation-dependent resolved shear stress on the leading and trailing partial dislocations, their potential nucleation sites and energy barriers. This reversible twinning-detwinning process accommodates large strains that can be beneficially utilized in applications requiring high ductility in addition to ultra-high strength.

Strength, Hardening, and Failure Observed by In Situ TEM Tensile Testing.

We present in situ transmission electron microscope tensile tests on focused ion beam fabricated single and multiple slip oriented Cu tensile samples with thicknesses in the range of 100-200 nm. Both crystal orientations fail by localized shear. While failure occurs after a few percent plastic strain and limited hardening in the single slip case, the multiple slip samples exhibit extended homogenous deformation and necking due to the activation of multiple dislocation sources in conjunction with significant hardening. The hardening behavior at 1% plastic strain is even more pronounced compared to compression samples of the same orientation due to the absence of sample taper and the interface to the compression platen. Moreover, we show for the first time that the strain rate sensitivity of such FIB prepared samples is an order of magnitude higher than that of bulk Cu.

Distinct host species correlate with Anaplasma phagocytophilum ankA gene clusters.

Anaplasma phagocytophilum is a gram-negative, tick-transmitted, obligate intracellular bacterium that elicits acute febrile diseases in humans and domestic animals. In contrast to the United States, human granulocytic anaplasmosis seems to be a rare disease in Europe despite the initial recognition of A. phagocytophilum as the causative agent of tick-borne fever in European sheep and cattle. Considerable strain variation has been suggested to occur within this species, because isolates from humans and animals differed in their pathogenicity for heterologous hosts. In order to explain host preference and epidemiological diversity, molecular characterization of A. phagocytophilum strains has been undertaken. Most often the 16S rRNA gene was used, but it might be not informative enough to delineate distinct genotypes of A. phagocytophilum. Previously, we have shown that A. phagocytophilum strains infecting Ixodes ricinus ticks are highly diverse in their ankA genes. Therefore, we sequenced the 16S rRNA and ankA genes of 194 A. phagocytophilum strains from humans and several animal species. Whereas the phylogenetic analysis using 16S rRNA gene sequences was not meaningful, we showed that distinct host species correlate with A. phagocytophilum ankA gene clusters.

Perylene-labeled silica nanoparticles: synthesis and characterization of three novel silica nanoparticle species for live-cell imaging.

The increasing exposure of humans to nanoscaled particles requires well-defined systems that enable the investigation of the toxicity of nanoparticles on the cellular level. To facilitate this, surface-labeled silica nanoparticles, nanoparticles with a labeled core and a silica shell, and a labeled nanoparticle network-all designed for live-cell imaging-are synthesized. The nanoparticles are functionalized with perylene derivatives. For this purpose, two different perylene species containing one or two reactive silica functionalities are prepared. The nanoparticles are studied by transmission electron microscopy, widefield and confocal fluorescence microscopy, as well as by fluorescence spectroscopy in combination with fluorescence anisotropy, in order to characterize the size and morphology of the nanoparticles and to prove the success and homogeneity of the labeling. Using spinning-disc confocal measurements, silica nanoparticles are demonstrated to be taken up by HeLa cells, and they are clearly detectable inside the cytoplasm of the cells.