Evaluating the effect of unidirectional loading on the piezoresistive characteristics of carbon nanoparticles.

The piezoresistive effect of materials can be adopted for a plethora of sensing applications, including force sensors, structural health monitoring, motion detection in fabrics and wearable, etc. Although metals are the most widely adopted material for sensors due to their reliability and affordability, they are significantly affected by temperature. This work examines the piezoresistive performance of carbon nanoparticle (CNP) bulk powders and discusses their potential applications based on strain-induced changes in their resistance and displacement. The experimental results are correlated with the characteristics of the nanoparticles, namely, dimensionality and structure. This report comprehensively characterizes the piezoresistive behavior of carbon black (CB), onion-like carbon (OLC), carbon nanohorns (CNH), carbon nanotubes (CNT), dispersed carbon nanotubes (CNT-D), graphite flakes (GF), and graphene nanoplatelets (GNP). The characterization includes assessment of the ohmic range, load-dependent electrical resistance and displacement tracking, a modified gauge factor for bulk powders, and morphological evaluation of the CNP. Two-dimensional nanostructures exhibit promising results for low loads due to their constant compression-to-displacement relationship. Additionally, GF could also be used for high load applications. OLC's compression-to-displacement relationship fluctuates, however, for high load it tends to stabilize. CNH could be applicable for both low and high loading conditions since its compression-to-displacement relationship fluctuates in the mid-load range. CB and CNT show the most promising results, as demonstrated by their linear load-resistance curves (logarithmic scale) and constant compression-to-displacement relationship. The dispersion process for CNT is unnecessary, as smaller agglomerates cause fluctuations in their compression-to-displacement relationship with negligible influence on its electrical performance.

The Influence of Adventitious Carbon Groups on the Wetting of Copper: A Study on the Effect of Microstructure on the Static Contact Angle.

Tuning of the wetting behavior of metallic surfaces by chemical and topographical modification has become popular in recent years. Still, there is a lack in the understanding of fundamental relations between intrinsic properties of the material and its resulting water contact angle. It is widely accepted in the literature that transitions from a hydrophilic to increasingly hydrophobic behavior upon exposure to ambient conditions happen due to the adsorption of adventitious hydrocarbons. In order to investigate the role of metallic bulk microstructure in the wetting behavior and its transition properties, we created three different grain sizes and deformation states on copper by preparation combined with heat treatment. We found that for freshly prepared surfaces, differences in the wetting behavior show a higher static contact angle for mechanically prepared surfaces with a fine-crystalline deformation layer compared to the electropolished cold-rolled copper sheet and the annealed defect-free coarse-grained surface. Already after five days of storage time, most of this difference vanishes, and all surfaces show a wetting behavior with a contact angle in the range of 97-100° after 30 days. Though long-term wetting behavior seems largely independent of microstructure, correlated XPS measurements showed an increased adsorption of organic contaminants of the mechanically polished surface. Preparation-induced near-surface defects seem to accelerate adsorption, while varying grain size and slight bulk deformation from rolling processes did not show significant effects. Complex relations between the amount of adsorbed carbon and the polarity of the adsorption film were found to depend on the sample age and influence the contact angle.

Surface Modification of Brass via Ultrashort Pulsed Direct Laser Interference Patterning and Its Effect on Bacteria-Substrate Interaction.

In recent decades, antibiotic resistance has become a crucial challenge for human health. One potential solution to this problem is the use of antibacterial surfaces, i.e., copper and copper alloys. This study investigates the antibacterial properties of brass that underwent topographic surface functionalization via ultrashort pulsed direct laser interference patterning. Periodic line-like patterns in the scale range of single bacterial cells were created on brass with a 37% zinc content to enhance the contact area for rod-shaped Escherichia coli (E. coli). Although the topography facilitates attachment of bacteria to the surface, reduced killing rates for E. coli are observed. In parallel, a high-resolution methodical approach was employed to explore the impact of laser-induced topographical and chemical modifications on the antibacterial properties. The findings reveal the underlying role of the chemical modification concerning the antimicrobial efficiency of the Cu-based alloy within the superficial layers of a few hundred nanometers. Overall, this study provides valuable insight into the effect of alloy composition on targeted laser processing for antimicrobial Cu-surfaces, which facilitates the thorough development and optimization of the process concerning antimicrobial applications.

Analysis of the carbide precipitation and microstructural evolution in HCCI as a function of the heating rate and destabilization temperature.

Microstructural modification of high chromium cast irons (HCCI) through the precipitation of secondary carbides (SC) during destabilization treatments is essential for improving their tribological response. However, there is not a clear consensus about the first stages of the SC precipitation and how both the heating rate (HR) and destabilization temperature can affect the nucleation and growth of SC. The present work shows the microstructural evolution, with a special focus on the SC precipitation, in a HCCI (26 wt% Cr) during heating up to 800, 900, and 980 °C. It was seen that the HR is the most dominant factor influencing the SC precipitation as well as the matrix transformation in the studied experimental conditions. Finally, this work reports for first time in a systematic manner, the precipitation of SC during heating of the HCCI, providing a further understanding on the early stages of the SC precipitation and the associated microstructural modifications.

Feasibility of Carbon Nanoparticle Coatings as Protective Barriers for Copper─Wetting Assessment.

Copper is extensively used in a wide range of industrial and daily-life applications, varying from heat exchangers to electrical wiring. Although it is protected from oxidation by its native oxide layer, when subjected to harsh environmental conditions─such as in coastal regions─this metal can rapidly degrade. Therefore, in this study, we analyze the potential use of carbon nanoparticle coatings as protective barriers due to their intrinsic hydrophobic wetting behavior. The nanocarbon coatings were produced via electrophoretic deposition on Cu platelets and characterized via scanning electron microscopy, confocal laser scanning microscopy, and sessile drop test; the latter being the primary focus since it provides insights into the wetting behavior of the produced coatings. Among the measured coatings, graphite flakes, graphene oxide, and carbon nanotube (CNT) coatings showed superhydrophobic behavior. Based on their wetting behavior, and specifically for electrical applications, CNT coatings showed the most promising results since these coatings do not significantly impact the substrate's electrical conductivity. Although CNT agglomerates do not affect the wetting behavior of the attained coatings, the coating's thickness plays an important role. Therefore, to completely coat the substrate, the CNT coating should be sufficiently thick─above approximately 1 µm.

An in-depth evaluation of sample and measurement induced influences on static contact angle measurements.

Static contact angle measurements are one of the most popular methods to analyze the wetting behavior of materials of any kind. Although this method is readily applicable without the need of sophisticated machinery, the results obtained for the very same material may vary strongly. The sensitivity of the measurement against environmental conditions, sample preparation and measurement conduction is a main factor for inconsistent results. Since often no detailed measurement protocols exist alongside published data, contact angle values as well as elaborated wetting studies do not allow for any comparison. This paper therefore aims to discuss possible influences on static contact angle measurements and to experimentally demonstrate the extent of these effects. Sample storage conditions, cleaning procedures, droplet volume, water grade and droplet application as well as the influence of evaporation on the static contact angle are investigated in detail. Especially sample storage led to differences in the contact angle up to 60%. Depending on the wetting state, evaporation can reduce the contact angle by 30-50% within 10 min in dry atmospheres. Therefore, this paper reviews an existing approach for a climate chamber and introduces a new measuring setup based on these results. It allows for the observation of the wetting behavior for several minutes by successfully suppressing evaporation without negatively affecting the surface prior to measurement by exposure to high humidity environments.

A FIB-SEM Based Correlative Methodology for X-Ray Nanotomography and Secondary Ion Mass Spectrometry: An Application Example in Lithium Batteries Research.

Correlative microscopy approaches are attracting considerable interest in several research fields such as materials and battery research. Recent developments regarding X-ray computer tomography have made this technique available in a compact module for scanning electron microscopes (SEMs). Nano-computed tomography (nanoCT) allows morphological analysis of samples in a nondestructive way and to generate 2D and 3D overviews. However, morphological analysis alone is not sufficient for advanced studies, and to draw conclusions beyond morphology, chemical analysis is needed. While conventional SEM-based chemical analysis techniques such as energy-dispersive X-ray spectroscopy (EDS) are adequate in many cases, they are not well suited for the analysis of trace elements and low-Z elements such as hydrogen or lithium. Furthermore, the large information depth in typical SEM-EDS imaging conditions limits the lateral resolution to micrometer length scales. In contrast, secondary ion mass spectrometry (SIMS) can perform elemental mapping with good surface sensitivity, nanoscale lateral resolution, and the possibility to analyze even low-Z elements and isotopes. In this study, we demonstrate the feasibility and compatibility of a novel FIB-SEM-based correlative nanoCT-SIMS imaging approach to correlate morphological and chemical data of the exact same sample volume, using a cathode material of a commercial lithium battery as an example.

Effectiveness of Direct Laser Interference Patterning and Peptide Immobilization on Endothelial Cell Migration for Cardio-Vascular Applications: An In Vitro Study.

Endothelial coverage of an exposed cardiovascular stent surface leads to the occurrence of restenosis and late-stent thrombosis several months after implantation. To overcome this difficulty, modification of stent surfaces with topographical or biochemical features may be performed to increase endothelial cells' (ECs) adhesion and/or migration. This work combines both strategies on cobalt-chromium (CoCr) alloy and studies the potential synergistic effect of linear patterned surfaces that are obtained by direct laser interference patterning (DLIP), coupled with the use of Arg-Gly-Asp (RGD) and Tyr-Ile-Gly-Ser-Arg (YIGSR) peptides. An extensive characterization of the modified surfaces was performed by using AFM, XPS, surface charge, electrochemical analysis and fluorescent methods. The biological response was studied in terms of EC adhesion, migration and proliferation assays. CoCr surfaces were successfully patterned with a periodicity of 10 µm and two different depths, D (≈79 and 762 nm). RGD and YIGSR were immobilized on the surfaces by CPTES silanization. Early EC adhesion was increased on the peptide-functionalized surfaces, especially for YIGSR compared to RGD. High-depth patterns generated 80% of ECs' alignment within the topographical lines and enhanced EC migration. It is noteworthy that the combined use of the two strategies synergistically accelerated the ECs' migration and proliferation, proving the potential of this strategy to enhance stent endothelialization.

Topography versus chemistry - How can we control surface wetting?

HYPOTHESIS: Wetting characterization and the production of engineered surfaces showing distinct contact angles or spreading behavior is of major importance for many industrial and scientific applications. As chemical composition plays a major role in the wetting behavior of flat samples, wettability, capillary forces and resulting droplet spreading on anisotropic surface patterns are expected to be highly dependent on surface chemistry as well. EXPERIMENTS: To gain understanding of the fundamental principles of the interplay between surface topography and surface chemistry regarding water wettability, anisotropic line patterns were produced on steel samples in a direct laser writing process. Homogeneous surface coatings allowed for a chemical masking of the laser patterns and therewith the identification of the influence of surface chemistry on static contact angles and wetting anisotropy. FINDINGS: While a carbon coating leads to pronounced wettability and spreading along the topographic anisotropy, an inert gold-palladium coating can fully suppress anisotropic droplet spreading. Model calculations show that an amorphous carbon coating leads to Wenzel wetting while the gold-palladium coating causes air inclusions between the water and the surface in the Cassie-Baxter wetting state. Only in combination with the right chemical composition of the surface, directional patterns show their potential of anisotropic wetting behavior.

Quantitative nanoscale imaging using transmission He ion channelling contrast: Proof-of-concept and application to study isolated crystalline defects.

A newly developed microscope prototype, namely npSCOPE, consisting of a Gas Field Ion Source (GFIS) column and a position sensitive Delay-line Detector (DLD) was used to perform Scanning Transmission Ion Microscopy (STIM) using keV He+ ions. One experiment used 25 keV ions and a second experiment used 30 keV ions. STIM imaging of a 50 nm thick free-standing gold membrane exhibited excellent contrast due to ion channelling and revealed rich microstructural features including isolated nanoscale twin bands which matched well with the contrast in the conventional ion-induced Secondary Electron (SE) imaging mode. Transmission Kikuchi Diffraction (TKD) and Backscattered Electron (BSE) imaging were performed on the same areas to correlate and confirm the microstructural features observed in STIM. Monte Carlo simulations of the ion and electron trajectories were performed with parameters similar to the experimental conditions to derive insights related to beam broadening and its effect in the degradation of transmission image resolution. For the experimental conditions used, STIM imaging showed a lateral resolution close to30 nm. Dark twin bands in bright grains as well as bright twin bands in dark grains were observed in STIM. Some of the twin bands were invisible in STIM. For the specific experimental conditions used, the ion transmission efficiency across a particular twin band was found to decrease by a factor of 2.8. Surprisingly, some grains showed contrast reversal when the Field of View (FOV) was changed indicating the sensitivity of the channelling contrast to even small changes in illumination conditions. These observations are discussed using ion channelling conditions and crystallographic orientations of the grains and twin bands. This study demonstrates for the first time the potential of STIM imaging using keV He+ ions to quantitatively investigate channelling in nanoscale structures including isolated crystalline defects.

Multipurpose setup used to characterize tribo-electrical properties of electrical contact materials.

Electrical contacts are pervasively found on countless modern devices and systems. It is imperative that connecting components present adequate electrical, mechanical, and chemical characteristics to fulfill the crucial role that they play in the system. To develop an electrical contact material that is tailored for a specific application, different approaches are pursued (e.g., coatings, reinforced composites, alloyed metals, duplex systems, etc.). The manufacturing of electrical contact materials demand a thorough characterization of their electrical properties, mechanical properties, and their resistance to wear, as well as their resistance to atmospheric conditions. Accordingly, commissioning of a novel setup enables a more comprehensive study of the materials that are developed. Therefore, a complete understanding of the material's electrical and tribological characteristics are attained, allowing the production of a material that is compliant with the particular demands of the application for which it is intended. This multipurpose setup was built with higher precision stages and higher accuracy 3-axis force sensor, thus providing the following improvement over the preceding setup:•Elevated load-bearing capacity (double), higher precision and stability.•Tribo-electrical characterization (implementation of scratch and fretting tests).•Environmental control (climate and external vibration).

A deep learning approach for complex microstructure inference.

Automated, reliable, and objective microstructure inference from micrographs is essential for a comprehensive understanding of process-microstructure-property relations and tailored materials development. However, such inference, with the increasing complexity of microstructures, requires advanced segmentation methodologies. While deep learning offers new opportunities, an intuition about the required data quality/quantity and a methodological guideline for microstructure quantification is still missing. This, along with deep learning's seemingly intransparent decision-making process, hampers its breakthrough in this field. We apply a multidisciplinary deep learning approach, devoting equal attention to specimen preparation and imaging, and train distinct U-Net architectures with 30-50 micrographs of different imaging modalities and electron backscatter diffraction-informed annotations. On the challenging task of lath-bainite segmentation in complex-phase steel, we achieve accuracies of 90% rivaling expert segmentations. Further, we discuss the impact of image context, pre-training with domain-extrinsic data, and data augmentation. Network visualization techniques demonstrate plausible model decisions based on grain boundary morphology.

Ni/Al-Hybrid Cellular Foams: An Interface Study by Combination of 3D-Phase Morphology Imaging, Microbeam Fracture Mechanics and In Situ Synchrotron Stress Analysis.

Nickel(Ni)/aluminium(Al) hybrid foams are Al base foams coated with Ni by electrodeposition. Hybrid foams offer an enhanced energy absorption capacity. To ensure a good adhering Ni coating, necessary for a shear resistant interface, the influence of a chemical pre-treatment of the base foam was investigated by a combination of an interface morphology analysis by focused ion beam (FIB) tomography and in situ mechanical testing. The critical energy for interfacial decohesion from these microbending fracture tests in the scanning electron microscope (SEM) were contrasted to and the results validated by depth-resolved measurements of the evolving stresses in the Ni coating during three-point bending tests at the energy-dispersive diffraction (EDDI) beamline at the synchrotron BESSY II. Such a multi-method assessment of the interface decohesion resistance with respect to the interface morphology provides a reliable investigation strategy for further improvement of the interface morphology.

Correlative Site-Specific Sample Preparation for Atom Probe Tomography on Complex Microstructures.

Site-specific specimen preparation for atom probe tomography (APT) is a challenging task. Small features need to be located using a suitable imaging technique and captured within a volume of less than 0.01 µm3. Correlative microscopy has shown to be helpful for target preparation as well as to gain complementary information about the material. Current strategies developed in that direction can be highly time-consuming and not always ensure the correct site extraction in complex microstructures. In this work, we present a methodology to study grain boundaries and interfaces in martensitic steels by combining electron backscattered diffraction, transmission Kikuchi diffraction (TKD), and APT. Furthermore, we include the design of a sample holder that allows to perform TKD and scanning transmission electron microscopy on the specimen during preparation without breaking the vacuum of the scanning electron microscope/focused ion beam workstation. We show a case study where a prior austenite grain boundary is traced from the bulk material to the apex of the APT specimen. The presence of contamination due to the specimen exposure to the electron beam and the use of plasma cleaning to minimize it are discussed.

Superior Wear-Resistance of Ti3C2Tx Multilayer Coatings.

Owing to MXenes' tunable mechanical properties induced by their structural and chemical diversity, MXenes are believed to compete with state-of-the-art 2D nanomaterials such as graphene regarding their tribological performance. Their nanolaminate structure offers weak interlayer interactions and an easy-to-shear ability to render them excellent candidates for solid lubrication. However, the acting friction and wear mechanisms are yet to be explored. To elucidate these mechanisms, 100-nm-thick homogeneous multilayer Ti3C2Tx coatings are deposited on technologically relevant stainless steel by electrospraying. Using ball-on-disk tribometry (Si3N4 counterbody) with acting contact pressures of about 300 MPa, their long-term friction and wear performance under dry conditions are studied. MXene-coated specimens demonstrate a 6-fold friction reduction and an ultralow wear rate (4 × 10-9 mm3 N-1 m-1) over 100 000 sliding cycles, outperforming state-of-the-art 2D nanomaterials by at least 200% regarding their wear life. High-resolution characterization verified the formation of a beneficial tribolayer consisting of thermally/mechanically degraded MXenes and amorphous/nanocrystalline iron oxides. The transfer of this tribolayer to the counterbody transforms the initial steel/Si3N4 contact to tribolayer/tribolayer contact with low shear resistance. MXene pileups at the wear track's reversal points continuously supply the tribological contact with fresh, lubricious nanosheets, thus enabling an ultra-wear-resistant and low-friction performance.

Particle encapsulation techniques for atom probe tomography of precipitates in microalloyed steels.

Atom probe tomography (APT) provides sub-nm resolution in the analysis of complex industrial steels. It can resolve the carbonitride precipitates in Nb-Ti microalloyed high-strength low-alloy (HSLA) steels that strongly affect material performance and illuminate the complex precipitation sequence before and during the thermo-mechanical controlled process (TMCP). However, the precipitate concentration is low in HSLA steels during austenite conditioning, especially at temperatures > 850 °C, so that the probability of detecting precipitates via APT is below 5%. Here, we demonstrate two encapsulation-based approaches that increase the precipitate concentration in the APT sample volume sufficiently to enable the analysis of sparse precipitates. The first method is based on metallographic etching and direct targeting of precipitates in the steel. A focused ion beam was used to mark precipitation sites. Encapsulation with nickel-phosphorus (Ni-P) enabled localized APT and increased the yield by a factor of 10. The second method relies on the chemical extraction of precipitates and subsequent encapsulation in a silicon oxide (SiOx) network at a very high particle density. Analysis of tips cut from the encapsulated particles increased the yield by a factor of >15. We discuss and compare the spatial and chemical accuracy obtained in the analysis of pure Nb-, Ti- and mixed Nb-Ti carbonitrides.

In-Depth Investigation of Copper Surface Chemistry Modification by Ultrashort Pulsed Direct Laser Interference Patterning.

Surface patterning in the micro- and nanometer-range by means of pulsed laser interference has repeatedly proven to be a versatile tool for surface functionalization. With these techniques, however, the surface is often changed not only in terms of morphology but also in terms of surface chemistry. In this study, we present an in-depth investigation of the chemical surface modification occurring during surface patterning of copper by ultrashort pulsed direct laser interference patterning (USP-DLIP). A multimethod approach of parallel analysis using visualizing, topography-sensitive, and spectroscopic techniques allowed a detailed quantification of surface morphology as well as composition and distribution of surface chemistry related to both processing and atmospheric aging. The investigations revealed a heterogeneous surface composition separated in peak and valley regions predominantly consisting of Cu2O, as well as superficial agglomerations of CuO and carbon species. The evaluation was supported by a modeling approach for the quantification of XPS results in relation to heterogeneous surface composition, which was observed by means of a combination of different spectroscopic techniques. The overall results provide a detailed understanding of the chemical and topographical surface modification during USP-DLIP, which allows a more targeted use of this technology for surface functionalization.

Objective homogeneity quantification of a periodic surface using the Gini coefficient.

The significance of periodic surface structuring methods, such as direct laser interference patterning, is growing steadily. Thus, the ability to objectively and consistently evaluate these surfaces is increasingly important. Standard parameters such as surface roughness or the arithmetic average height are meant to quantify the deviation of a real surface from an ideally flat one. Periodically patterned surfaces, however, are an intentional deviation from that ideal. Therefore, their surface profile has to be separated into a periodic and a non-periodic part. The latter can then be analyzed using the established surface parameters and the periodic nature allows a quantification of structure homogeneity, e.g. based on Gini coefficient. This work presents a new combination of established methods to reliably and objectively evaluate periodic surface quality. For this purpose, the periodicity of a given surface is extracted by Fourier analysis, and its homogeneity with respect to a particular property is determined for the repeating element via a Gini analysis. The proposed method provides an objective and reliable instrument for evaluating the surface quality for the selected attribute regardless of the user. Additionally, this technique can potentially be used to both identify a suitable surface structuring technique and determine the optimal process parameters.