Metals by Micro‐Scale Additive Manufacturing: Comparison of Microstructure and Mechanical Properties

Many emerging applications in microscale engineering rely on the fabrication of 3D architectures in inorganic materials. Small‐scale additive manufacturing (AM) aspires to provide flexible and facile access to these geometries. Yet, the synthesis of device‐grade inorganic materials is still a key challenge toward the implementation of AM in microfabrication. Here, a comprehensive overview of the microstructural and mechanical properties of metals fabricated by most state‐of‐the‐art AM methods that offer a spatial resolution ≤10 μm is presented. Standardized sets of samples are studied by cross‐sectional electron microscopy, nanoindentation, and microcompression. It is shown that current microscale AM techniques synthesize metals with a wide range of microstructures and elastic and plastic properties, including materials of dense and crystalline microstructure with excellent mechanical properties that compare well to those of thin‐film nanocrystalline materials. The large variation in materials' performance can be related to the individual microstructure, which in turn is coupled to the various physico‐chemical principles exploited by the different printing methods. The study provides practical guidelines for users of small‐scale additive methods and establishes a baseline for the future optimization of the properties of printed metallic objects—a significant step toward the potential establishment of AM techniques in microfabrication.     

In situ hybridization studies confirming recent findings of the existence of a local nonneuronal catecholamine production in human patellar tendinosis

We have in recent studies presented unexpected immunohistochemical evidence favoring the existence of a local production of catecholamines, and an occurrence of adrenergic receptors on the tendon cells (tenocytes), in the human patellar tendon. This was particularly noticed for tendons from patients suffering from tendinosis (chronic tendon pain), which has led us to propose an involvement of this autocrine/paracrine system in the development of tendinosis, especially since catecholamines have been reported to be modulators of tissue remodeling and pain processes. However, the findings concerning catecholamine production have so far only been noted at the level of protein detection, and for this reason, the aim of the present study was to confirm the previous immunohistochemical results by using in situ hybridization (ISH) technique. A ssDNA probe detecting human mRNA for the catecholamine-synthesizing enzyme tyrosine hydroxylase (TH) was applied. The ISH results revealed that there were clear reactions indicating the existence of mRNA for TH in tenocytes of tendinosis specimens. It was generally noted that disfigured tenocytes were the ones with the most distinct reactions, while normally looking tenocytes hardly displayed any reactions at all. In conclusion, this study presents the first evidence at the mRNA level of the existence of a local nonneuronal production of catecholamines in human patellar tendon tissue. The findings add to recent observations of the occurrence of a local production in tendons of signal substances traditionally related to neurons.     

X‐ray Structures and Feasibility Assessment of CLK2 Inhibitors for Phelan–McDermid Syndrome

CLK2 inhibition has been proposed as a potential mechanism to improve autism and neuronal functions in Phelan–McDermid syndrome (PMDS). Herein, the discovery of a very potent indazole CLK inhibitor series and the CLK2 X‐ray structure of the most potent analogue are reported. This new indazole series was identified through a biochemical CLK2 Caliper assay screen with 30k compounds selected by an in silico approach. Novel high‐resolution X‐ray structures of all CLKs, including the first CLK4 X‐ray structure, bound to known CLK2 inhibitor tool compounds (e.g., TG003, CX‐4945), are also shown and yield insight into inhibitor selectivity in the CLK family. The efficacy of the new CLK2 inhibitors from the indazole series was demonstrated in the mouse brain slice assay, and potential safety concerns were investigated. Genotoxicity findings in the human lymphocyte micronucleus test (MNT) assay are shown by using two structurally different CLK inhibitors to reveal a major concern for pan‐CLK inhibition in PMDS.     

A Cocatalytic Electron‐Transfer Cascade Site‐Selectively Placed on TiO2 Nanotubes Yields Enhanced Photocatalytic H2 Evolution

Separation and transfer of photogenerated charge carriers are key elements in designing photocatalysts. TiO₂ in numerous geometries has been for many years the most studied photocatalyst. To overcome kinetic limitations and achieve swift charge transfer, TiO₂ has been widely investigated with cocatalysts that are commonly randomly placed nanoparticles on a TiO₂ surface. The poor control over cocatalyst placement in powder technology approaches can drastically hamper the photocatalytic efficiencies. Here in contrast it is shown that the site‐selective placement of suitable charge‐separation and charge‐transfer cocatalysts on a defined TiO₂ nanotube morphology can provide an enhancement of the photocatalytic reactivity. A TiO₂–WO₃–Au electron‐transfer cascade photocatalyst is designed with nanoscale precision for H₂ production on TiO₂ nanotube arrays. Key aspects in the construction are the placement of the WO₃/Au element at the nanotube top by site‐selective deposition and self‐ordered thermal dewetting of Au. In the ideal configuration, WO₃ acts as a buffer layer for TiO₂ conduction band electrons, allowing for their efficient transfer to the Au nanoparticles and then to a suitable environment for H₂ generation, while TiO₂ holes due to intrinsic upward band bending in the nanotube walls and short diffusion length undergo a facilitated transfer to the electrolyte where oxidation of hole‐scavenger molecules takes place. These photocatalytic structures can achieve H₂ generation rates significantly higher than any individual cocatalyst–TiO₂ combination, including a classic noble metal–TiO₂ configuration.     

A time delay method to solve non-collocated input estimation problems

Fundamental properties of using time delay to solve ill-posed input estimation problems are studied. It is shown that for systems with non-collocated sensors and inputs these problems are ill-posed, and how a sensor-specific time delay approach can be used to formulate a modified, well-posed problem. Invertibility of the associated block Toeplitz matrix and its relation to truncation errors are discussed. Moreover, it is shown that the time delay approach, in order to produce an acceptable solution, requires that certain conditions regarding the positioning of sensors are fulfilled. Some numerical examples to illustrate various aspects of the time delay approach are also given. The issues are treated in the setting of mechanical systems.     

Soluble polyelectrolyte complexes composed of poly(ethylene oxide)-block-poly(sodium methacrylate) and poly(methacryloyloxyethyl trimethylammonium chloride)

Complexation between poly(methacryloyloxyethyl trimethylammonium chloride), PMOTAC, and poly(ethylene oxide)-block-poly(sodium methacrylate), PEO-block-PMANa with MANa blocks with two different molecular weights has been investigated by light scattering, LS, viscosimetry and conductivity measurements. Owing to the PEO blocks the polyelectrolyte complexes are water-soluble particles. Effects of the ratio of the oppositely charged monomer units, the ionic strength of the solution, and solution pH have been studied. With the 1:1 mixing ratio stable polyelectrolyte complexes, PECs, with spherical shape were formed. When either the cationic or anionic component was in excess, charged non-stoichiometric complexes were formed. The complexes were stable also in solutions with comparatively high ionic strength, though stronger secondary aggregation was observed. By changing the solution pH the degree of dissociation of PEO-block-PMANa could be adjusted. In the vicinity of the pK_a,average of PMAA, a minimum in the particle size and a maximum in the solution conductivity were observed. In solutions with lower pH, a typical self-complexation of PEO-block-PMAA was detected. Also, unexpected interactions between PMOTAC and the self-complexes of PEO-block-PMAA were observed.     

Autofocusing in digital holographic phase contrast microscopy on pure phase objects for live cell imaging

Digital holography enables a multifocus quantitative phase microscopy for the investigation of reflective surfaces and for marker-free live cell imaging. For digital holographic long-term investigations of living cells an automated (subsequent) robust and reliable numerical focus adjustment is of particular importance. Four numerical methods for the determination of the optimal focus position in the numerical reconstruction and propagation of the complex object waves of pure phase objects are characterized, compared, and adapted to the requirements of digital holographic microscopy. Results from investigations of an engineered surface and human pancreas tumor cells demonstrate the applicability of Fourier-weighting- and gradient-operator-based methods for robust and reliable automated subsequent numerical digital holographic focusing.     

Modelling of ductile fracture initiation in strength mismatched welded joint

In this paper, the effect of strength mismatch and width of the welded joints on the stress–strain distribution in the crack tip region has been discussed. The single-edge notched bend (SENB) specimens (precrack length a₀/W = 0.32) were experimentally and numerically analysed. The model of local approach to fracture, proposed by Gurson, Tvergaard and Needleman, was used. High-strength low-alloyed (HSLA) steel was used as a base metal in quenched and tempered condition. The flux-cored arc-welding process in shielding gas was used. Two different fillers were selected to make over- and undermatched weld metal. The experimental analysis of fracture behaviour of the over- and undermatched welded joints was followed by numerical computations of void volume fraction in front of the crack tip. The critical void volume fraction, f_c, used in prediction of the crack growth initiation on the SENB specimen had been previously determined on a round smooth specimen. Three widths of weld metal were considered: 6, 12 and 18 mm. A comparison of the crack tip opening displacement (CTOD) values corresponding to crack initiation in the SENB specimens is given, as determined both experimentally and using the GTN model.     

Coupled HM effects in a crystalline rock mass due to glaciation: indicative results from groundwater flow regimes and stresses from an FEM study

This paper highlights certain aspects of glacial impact on groundwater flow and rock mechanics, of particular interest in future scenarios for the geological disposal of nuclear waste. The investigation took the form of a generic exercise based on conditions at the underground research facility in Whiteshell, Canada. The site scale model domain boundaries were set up based on a number of major deformation zones. The surface boundary conditions comprised a transient ice sheet load and related hydraulic heads, generated by meltwater. It has thus been possible to compare glacial impact in relation to present-day climatological conditions. The main issues in the investigation were to evaluate the groundwater flow regime and the pre-requisites for underground jacking as well as shearing according to the prescribed geoscientific properties of a benchmark protocol. Special attention has been devoted to a solution to the hydromechanical (HM) problem (1) with or without process coupling, (2) with or without a transient approach, and (3) considering a two- or three-dimensional mode. The study underlines the need for transient analyses in 3D of these coupled phenomena.      

Novel weakly coordinating heterocyclic anions for use in lithium batteries

Ab initio calculations have been performed for a new family of lithium salts based on heterocyclic anions: [CF₃SON₄C_2n]⁻ (0 ≤ n ≤ 4). In total, 10 different anions and their 1:1 ion pairs with lithium ions have been studied. The lithium ion affinity globally decreases with the degree of CN-substitution to the ring. Bidentate lithium ion coordination to the sulfonyl oxygen atom and one additional atom or to two adjacent ring nitrogen atoms is strongly preferred when structurally possible. The extremely low lithium ion affinities of the anions together with an appreciable stability towards oxidation make these salts possible candidates for future lithium battery electrolytes.