Temperature-Adaptive Ultralubricity of a WS2/a-C Nanocomposite Coating: Performance from Room Temperature up to 500 °C.

This study reports on the ultralubricity of a high-temperature resilient nanocomposite WS2/a-C tribocoating. The coefficient of friction of this coating remains at around 0.02 independently of a thermal treatment up to ∼500 °C, as confirmed by high-temperature tribotests. Moreover, the coating annealed at 450 °C keeps exhibiting a similar ultralubricity when cooled back down to room temperature and tested there, implying a tribological self-adaptation over a broad temperature range. High-resolution TEM observations of the tribofilms on the wear track unveil that WS2 nanoplatelets form dynamically via atomic rearrangement and extend via unfaulting geometrical defects (bound by partial climb dislocations). The (002) basal planes of the WS2 nanoplatelets, reoriented parallel to the tribo-sliding direction, contribute to a sustainable ultralubricity. The declining triboperformance beyond 500 °C is associated with sulfur loss rather than the transformation of WS2 into inferior WO3 via oxidation as suggested earlier. This self-adaptive WS2/a-C tribocoating holds promise for a constant ultralubrication with excellent thermal performance.

Using X-Ray Scattering to Elucidate the Microstructural Instability of 3D Bicontinuous Nanoporous Metal Scaffolds for Use in an Aperiodic 3D Tricontinuous Conductor-Insulator-Conductor Nanocapacitor.

The development of three-dimensional aperiodic energy storage devices is in part impeded by the lack of appropriate aperiodic templates that can withstand the thermal conditions required to deposit energy storage materials within their void space. Herein, the feasibility of an aperiodic three-dimensional architecture for energy storage is demonstrated for the first time by constructing a tricontinuous conductor-insulator-conductor (CIC) nanocapacitor on an aperiodic nanoporous gold scaffold. To accomplish this, the scaffold was characterized using in situ small-angle X-ray scattering (SAXS) during exposure to a thermal environment, revealing that its microstructure eventually stabilizes after undergoing a phase of rapid coarsening, indicating a departure from the 1/4 time-dependent power-law coarsening behavior usually observed at the early stage of the coarsening process. Using this stability regime, we created the CIC by intentionally precoarsening and stabilizing the scaffold before depositing two dissimilar metal oxide films in its void space by atomic layer deposition. Current-voltage characteristics and electrochemical impedance spectroscopy measurements revealed that the un-optimized 3D CIC outperformed its 2D counterpart by ∼4× in terms of capacitance. This proof-of-concept device will pave the way to the development of aperiodic three-dimensional energy storage systems with enhanced energy and power densities.

Depth Profile Analysis of Thin Oxide Layers on Polycrystalline Fe-Cr.

Surfaces of polycrystalline ferritic Fe-Cr steel with grain sizes of about 13 µm in diameter were investigated with surface sensitive techniques. Thin oxide layers, with a maximum thickness of about 100 nm, were grown by oxidation in air at temperatures up to 450°C and were subsequently characterized using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy. Correlative microscopy was applied, which allows for element-specific depth profiles on selected grains with a particular crystal orientation. A strong correlation between the grain orientation and the thickness of the oxide layer was found. The sequence in the oxidation growth rate of ferritic Fe-Cr steel crystal planes is found to be {011} > {111} > {001}, which is unexpectedly opposed to known Fe-based systems. Moreover, for the first time, the Cr/Fe ratio throughout the oxide layer has been determined per grain orientation. A clear order from high to low of {001} > {111} > {011} was detected.

In Situ High-Temperature EBSD and 3D Phase Field Studies of the Austenite-Ferrite Transformation in a Medium Mn Steel.

In this research, in situ high-temperature electron backscattered diffraction (EBSD) mapping is applied to record and analyze the migration of the α/γ interfaces during cyclic austenite-ferrite phase transformations in a medium manganese steel. The experimental study is supplemented with related 3D phase field (PF) simulations to better understand the 2D EBSD observations in the context of the 3D transformation events taking place below the surface. The in situ EBSD observations and PF simulations show an overall transformation behavior qualitatively similar to that measured in dilatometry. The behavior and kinetics of individual austenite-ferrite interfaces during the transformation is found to have a wide scatter around the average interface behavior deduced on the basis of the dilatometric measurements. The trajectories of selected characteristic interfaces are analyzed in detail and yield insight into the effect of local conditions in the vicinity of interfaces on their motion, as well as the misguiding effects of 2D observations of processes taking place in 3D.

Gaining sight after being blind: A tribute to Jing Zhu.

This contribution to the Festschrift for Professor Jing Zhu concentrates on in-situ electron microscopy, a topic which is key in her scientific work. In particular this paper delineates the possibilities of utilizing in-situ transmission electron microscopy to unravel size effects in the structure-property relationship. We have focused on in-situ compression, tension and cyclic fatigue experiments on non-crystalline metallic materials, also called metallic glasses (MG). In-situ quantitative compression tests revealed intrinsic and strong size effects of taper-free metallic glass nanopillars inside a transmission electron microscope (TEM) on different MG compositions. The deformation is defect-nucleation-controlled in larger pillars but becomes propagation-controlled in smaller pillars. A unique increase in strength and strain hardening was observed for smaller sized specimens in tension which is different compared to compression experiments with the same MG compositions. Under cyclic loading a very interesting new phenomenon was observed of increasing deformability depending on the number of cycles and size. The increase in deformability increases with increasing diameter whereas the number of cycles to reach half of the peak stress is decreasing with increasing diameter. The proposed experimental technique of loading and unloading cycles opens a new route to increase the ductility of metallic glasses.

Template-Free Synthesis of Nanoporous Nickel and Alloys as Binder-Free Current Collectors of Li Ion Batteries.

This paper reports a versatile template-free method based on the hydrogen reduction of metallic salts for the synthesis of nanoporous Ni and alloys. The approach involves thermal decomposition and reduction of metallic precursors followed with metal cluster nucleation and ligament growth. Topological disordered porous architectures of metals with a controllable distribution of pore size and ligament size ranging from tens of nanometers to micrometers are synthesized. The reduction processes are scrutinized through X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The formation mechanism of the nanoporous metal is qualitatively explained. The as-prepared nanoporous Ni was tested as binder-free current collectors for nickel oxalate anodes of lithium ion batteries. The nanoporous Ni electrodes deliver enhanced reversible capacities and cyclic performances compared with commercial Ni foam. It is confirmed that this synthesis method has versatility not only because it is suitable for different types of metallic salts precursors but also for various other metals and alloys.

Formation of Nanoporous Gold Studied by Transmission Electron Backscatter Diffraction.

Transmission electron backscatter diffraction (t-EBSD) was used to investigate the effect of dealloying on the microstructure of 140-nm thin gold foils. Statistical and local comparisons of the microstructure between the nonetched and nanoporous gold foils were made. Analyses of crystallographic texture, misorientation distribution, and grain structure clearly prove that during the dealloying manufacturing process of nanoporous materials the crystallographic texture is enhanced significantly with a clear decrease of internal strain, whereas maintaining the grain structure.

Gyroid nickel nanostructures from diblock copolymer supramolecules.

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template's channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

Microscopic characterisation of suspended graphene grown by chemical vapour deposition.

We present a multi-technique characterisation of graphene grown by chemical vapour deposition (CVD) and thereafter transferred to and suspended on a grid for transmission electron microscopy (TEM). The properties of the electronic band structure are investigated by angle-resolved photoelectron spectromicroscopy, while the structural and crystalline properties are studied by TEM and Raman spectroscopy. We demonstrate that the suspended graphene membrane locally shows electronic properties comparable with those of samples prepared by micromechanical cleaving of graphite. Measurements show that the area of high quality suspended graphene is limited by the folding of the graphene during the transfer.

Metallic muscles at work: high rate actuation in nanoporous gold/polyaniline composites.

Metallic muscles made of nanoporous metals suffer from serious drawbacks caused by the usage of an aqueous electrolyte for actuation. An aqueous electrolyte prohibits metallic muscles from operating in dry environments and hampers a high actuation rate due to the low ionic conductivity of electrolytes. In addition, redox reactions involved in electrochemical actuation severely coarsen the ligaments of nanoporous metals, leading to a substantial loss in performance of the actuator. Here we present an electrolyte-free approach to put metallic muscles to work via a metal/polymer interface. A nanocoating of polyaniline doped with sulfuric acid was grown onto the ligaments of nanoporous gold. Dopant sulfate anions coadsorbed into the polymer coating matrix were exploited to tune the nanoporous metal surface stress and subsequently generate macroscopic dimensional changes in the metal. Strain rates achieved in the single-component nanoporous metal/polymer composite actuator are 3 orders of magnitude higher than that of the standard three-component nanoporous metal/electrolyte hybrid actuator.

Molecule-by-molecule writing using a focused electron beam.

The resolution of lithography techniques needs to be extended beyond their current limits to continue the trend of miniaturization and enable new applications. But what is the ultimate spatial resolution? It is known that single atoms can be imaged with a highly focused electron beam. Can single atoms also be written with an electron beam? We verify this with focused electron-beam-induced deposition (FEBID), a direct-write technique that has the current record for the smallest feature written by (electron) optical lithography. We show that the deposition of an organometallic precursor on graphene can be followed molecule-by-molecule with FEBID. The results show that mechanisms that are inherent to the process inhibit a further increase in control over the process. Hence, our results present the resolution limit of (electron) optical lithography techniques. The writing of isolated, subnanometer features with nanometer precision can be used, for instance, for the local modification of graphene and for catalysis.

Selective functionalization of tailored nanostructures.

The controlled positioning of nanostructures with active molecular components is of importance throughout nanoscience and nanotechnology. We present a novel three-step method to produce nanostructures that are selectively decorated with functional molecules. We use fluorophores and nanoparticles to functionalize SiO features with defined shapes and with sizes ranging from micrometers to 25 nm. The method is called MACE-ID: molecular assembly controlled by electron-beam-induced deposition. In the first step, SiO nanostructures are written with focused electron-beam-induced deposition, a direct-writing technique. In the second step, the deposits are selectively silanized. In the final step, the silanes are functionalized with fluorescent dyes, polystyrene spheres, or gold nanoparticles. This recipe gives exciting new possibilities for combining the highly accurate control of top-down patterning (e-beam direct writing) with the rich variety of the bottom-up approach (self-assembly), leading to active or responsive surfaces. An important advantage of MACE-ID is that it can be used on substrates that already contain complex features, such as plasmonic structures, nanoantennas, and cavities.

Enhanced strain in functional nanoporous gold with a dual microscopic length scale structure.

We have synthesized nanoporous Au with a dual microscopic length scale by exploiting the crystal structure of the alloy precursor. The synthesized mesoscopic material is characterized by stacked Au layers of submicrometer thickness. In addition, each layer displays nanoporosity through the entire bulk. It is shown that the thickness of these layers can be tailored via the grain size of the alloy precursor. The two-length-scale structure enhances the functional properties of nanoporous gold, leading to charge-induced strains of amplitude up to 6%, which are roughly 2 orders of magnitude larger than in nanoporous Au with the standard one-length-scale porous morphology. A model is presented to describe these phenomena.

Supramolecular route to well-ordered metal nanofoams.

Metal nanofoams with a porosity above 50% v/v have recently attracted great interest in materials science due to their interesting properties. We demonstrate a new straightforward route to prepare such nanofoams using diblock copolymer-based PS-block-P4VP(PDP) supramolecules that self-assemble into a bicontinuous gyroid morphology, consisting of PS network channels in a P4VP(PDP) matrix. After dissolving the PDP, the P4VP collapses onto the PS struts and a free-standing bicontinuous gyroid template of 50-100 µm thickness and interconnected, uniformly sized pores is formed. The hydrophilic P4VP corona facilitates the penetration of water-based plating reagents into the porous template and enables a successful metal deposition. After plating, the polymer is simply degraded by heating, resulting in a well-ordered inverse gyroid nickel foam. Essential to this approach is the removal of only one part of the matrix (i.e., PDP). Therefore, the template accounts for 50% v/v or more. The porosity characteristics (amount, size of pores) can be tuned by selecting the appropriate copolymer and by adjusting the amount of PDP.

Advances in transmission electron microscopy: in situ straining and in situ compression experiments on metallic glasses.

In the field of transmission electron microscopy (TEM), fundamental and practical reasons still remain that hamper a straightforward correlation between microscopic structural information and deformation mechanisms in materials. In this article, it is argued that one should focus in particular on in situ rather than on postmortem observations of the microstructure. This viewpoint has been exemplified with in situ straining and in situ compression studies on metallic glasses. In situ TEM straining of amorphous metals permits an evaluation of the thickness of the liquid-like layer (LLL) formed because of heat evolution after shear band development. The experimental evaluation confirms that the thickness of a LLL present at the last moment of fracture substantially exceeds the generally accepted thickness of a shear band. In situ TEM and in situ SEM compression experiments on metallic glass pillars lead to the conclusion that smaller sized pillars deform more homogeneously than larger sized pillars.

Ultrasoft magnetic films investigated with Lorentz tranmission electron microscopy and electron holography.

As a tribute to the scientific work of Professor Gareth Thomas in the field of structure-property relationships this paper delineates a new possibility of Lorentz transmission electron microscopy (LTEM) to study the magnetic properties of soft magnetic films. We show that in contrast to the traditional point of view, not only does the direction of the magnetization vector in nano-crystalline films make a correlated small-angle wiggling, but also the magnitude of the magnetization modulus fluctuates. This fluctuation produces a rapid modulation in the LTEM image. A novel analysis of the ripple structure in nano-crystalline Fe-Zr-N film corresponds to an amplitude of the transversal component of the magnetization deltaMy of 23 mT and a longitudinal fluctuation of the magnetization of the order of deltaMx = 30 mT. The nano-crystalline (Fe99Zr1)1-xNx films have been prepared by DC magnetron reactive sputtering with a thickness between 50 and 1000 nm. The grain size decreased monotonically with N content from typically 100 nm in the case of N-free films to less than 10 nm for films containing 8 at%. The specimens were examined with a JEOL 2010F 200 kV transmission electron microscope equipped with a post column energy filter (GIF 2000 Gatan Imaging Filter). For holography, the microscope is mounted with a biprism (JEOL biprism with a 0.6 microm diameter platinum wire).