Influence of Processing Route on the Surface Reactivity of Cu47Ti33Zr11Ni6Sn2Si1 Metallic Glass

Recently, laser additive manufacturing (AM) techniques have emerged as a promising alternative for the synthesis of bulk metallic glasses (BMGs) with massively increased freedom in part size and geometry, thus extending their economic applicability of this material class. Nevertheless, porosity, compositional inhomogeneity, and crystallization display themselves to be the emerging challenges for this processing route. The impact of these “defects” on the surface reactivity and susceptibility to corrosion was seldom investigated but is critical for the further development of 3D-printed BMGs. This work compares the surface reactivity of cast and additively manufactured (via laser powder bed fusion—LPBF) Cu47Ti33Zr11Ni6Sn2Si1 metallic glass after 21 days of immersion in a corrosive HCl solution. The cast material presents lower oxygen content, homogeneous chemical distribution of the main elements, and the surface remains unaffected after the corrosion experimentation based on vertical scanning interferometry (VSI) investigation. On the contrary, the LPBF material presents a considerably higher reactivity seen through crack propagations on the surface. It exhibits higher oxygen content, heterogeneous chemical distribution, and presence of defects (porosity and cracks) generated during the manufacturing process.

Performance Analysis of Surface Reconstruction Algorithms in Vertical Scanning Interferometry Based on Coherence Envelope Detection

Optical interferometry plays an important role in the topographical surface measurement and characterization in precision/ultra-precision manufacturing. An appropriate surface reconstruction algorithm is essential in obtaining accurate topography information from the digitized interferograms. However, the performance of a surface reconstruction algorithm in interferometric measurements is influenced by environmental disturbances and system noise. This paper presents a comparative analysis of three algorithms commonly used for coherence envelope detection in vertical scanning interferometry, including the centroid method, fast Fourier transform (FFT), and Hilbert transform (HT). Numerical analysis and experimental studies were carried out to evaluate the performance of different envelope detection algorithms in terms of measurement accuracy, speed, and noise resistance. Step height standards were measured using a developed interferometer and the step profiles were reconstructed by different algorithms. The results show that the centroid method has a higher measurement speed than the FFT and HT methods, but it can only provide acceptable measurement accuracy at a low noise level. The FFT and HT methods outperform the centroid method in terms of noise immunity and measurement accuracy. Even if the FFT and HT methods provide similar measurement accuracy, the HT method has a superior measurement speed compared to the FFT method.

The Dissolution Rate of CaCO3 in the Ocean

The dissolution of CaCO3 minerals in the ocean is a fundamental part of the marine alkalinity and carbon cycles. While there have been decades of work aimed at deriving the relationship between dissolution rate and mineral saturation state (a so-called rate law), no real consensus has been reached. There are disagreements between laboratory- and field-based studies and differences in rates for inorganic and biogenic materials. Rates based on measurements on suspended particles do not always agree with rates inferred from measurements made near the sediment–water interface of the actual ocean. By contrast, the freshwater dissolution rate of calcite has been well described by bulk rate measurements from a number of different laboratories, fit by basic kinetic theory, and well studied by atomic force microscopy and vertical scanning interferometry to document the processes at the atomic scale. In this review, we try to better unify our understanding of carbonate dissolution in the ocean via a relatively new, highly sensitive method we have developed combined with a theoretical framework guided by the success of the freshwater studies. We show that empirical curve fits of seawater data as a function of saturation state do not agree, largely because the curvature is itself a function of the thermodynamics. Instead, we show that models that consider both surface energetic theory and the complicated speciation of seawater and calcite surfaces in seawater are able to explain most of the most recent data.This new framework can also explain features of the historical data that have not been previously explained. The existence of a kink in the relationship between rate and saturation state, reflecting a change in dissolution mechanism, may be playing an important role in accelerating CaCO3 dissolution in key sedimentary environments.

Etch pit distribution on calcite cleavage surfaces – experiments and simulation

<p>During the dissolution at a calcite cleavage face, etch pits open around defects. Atomic steps moving outwards from these pit centres are currently considered the general driving mechanism of this dissolution process that results in heterogeneous material flux from the surface. This means that the defects that generate the etch pits are crucial for the surface evolution. Recent kinetic Monte Carlo (kMC) simulation results indicate that not only the density but also the spatial distribution of defects is critical for the influence on dissolution.</p><p>In kMC simulations used for crystal dissolution, defect positions are input and can be defined in various ways, e.g., at pre-defined coordinates or randomly drawn from a distribution. The user is free in defining the defects, although it can generally be considered reasonable to choose defect densities and distributions as close as possible to what is expected to occur in nature and technical systems.</p><p>The actual spatial distribution of screw dislocations in calcite and their influence on rate variability are still not entirely known. To make the calcite kMC simulations comparable with experimental results, we experimentally determined the etch pit distributions, analyzed them and subsequently used them as input for further kMC studies.</p><p>While the direct measurement of defects in the crystal structure is extremely difficult, the indirect approach of measuring etch pits that have formed around defect outcrops during the beginning of dissolution is more feasible. For this, cleaved calcite single crystals were etched using ultra-pure water for 3 to 4 hours to obtain a significant amount of etch pits on the surface. The topography of the crystal surfaces was analysed using Vertical Scanning Interferometry (VSI). The resulting topography maps were stitched to gain a larger area for better statistics, and the centres of visible etch pits marked. This generates two-dimensional point patterns that describe the actual defect distribution more accurately than purely randomly generated coordinates without further constraints.</p><p>Based on data analysis of the experiments, we will show the resulting point distributions and synthetic patterns with similar underlying statistics. Using these as input for modelling, we then calculate kMC simulations and geometrical models of a system close to the calcite single crystal from our experiment, and compare them also to simulations using different defect positions as input.</p>

A Statistical Approach for Analysis of Dissolution Rates Including Surface Morphology

Understanding mineral dissolution is relevant for natural and industrial processes that involve the interaction of crystalline solids and fluids. The dissolution of slow dissolving minerals is typically surface controlled as opposed to diffusion/transport controlled. At these conditions, the dissolution rate is no longer constant in time or space, an outcome observed in rate maps and correspondent rate spectra. The contribution and statistical prevalence of different dissolution mechanisms is not known. Aiming to contribute to close this gap, we present a statistical analysis of the variability of calcite dissolution rates at the nano- to micrometer scale. A calcite-cemented sandstone was used to perform flow experiments. Dissolution of the calcite-filled rock pores was measured using vertical scanning interferometry. The resultant types of surface morphologies influenced the outcome of dissolution. We provide a statistical description of these morphologies and show their temporal evolution as an alternative to the lack of rate spatial variability in rate constants. Crystal size impacts dissolution rates most probably due to the contribution of the crystal edges. We propose a new methodology to analyze the highest rates (tales of rate spectra) that represent the formation of deeper etch pits. These results have application to the parametrization and upscaling of geochemical kinetic models, the characterization of industrial solid materials and the fundamental understanding of crystal dissolution.

Vertical Scanning Interferometry for Label-Free Detection of Peptide-Antibody Interactions

Peptide microarrays are a fast-developing field enabling the mapping of linear epitopes in the immune response to vaccinations or diseases and high throughput studying of protein-protein interactions. In this respect, a rapid label-free measurement of protein layer topographies in the array format is of great interest but is also a great challenge due to the extremely low aspect ratios of the peptide spots. We have demonstrated the potential of vertical scanning interferometry (VSI) for a detailed morphological analysis of peptide arrays and binding antibodies. The VSI technique is shown to scan an array area of 5.1 square millimeters within 3–4 min at a resolution of 1.4 μm lateral and 0.1 nm vertical in the full automation mode. Topographies obtained by VSI do match the one obtained by AFM measurements, demonstrating the accuracy of the technique. A detailed topology of peptide-antibody layers on single spots was measured. Two different measurement regions are distinguished according to the antibody concentration. In the case of weakly diluted serum, the thickness of the antibody layer is independent of the serum dilution and corresponds to the physical thickness of the accumulated antibody layer. In strongly diluted serum, the thickness measured via VSI is linearly proportional to the serum dilution.

Towards Functional Silicon Nitride Coatings for Joint Replacements

Silicon nitride (SiNx) coatings are currently under investigation as bearing surfaces for joint implants, due to their low wear rate and the good biocompatibility of both coatings and their potential wear debris. The aim of this study was to move further towards functional SiNx coatings by evaluating coatings deposited onto CoCrMo surfaces with a CrN interlayer, using different bias voltages and substrate rotations. Reactive direct current magnetron sputtering was used to coat CoCrMo discs with a CrN interlayer, followed by a SiNx top layer, which was deposited by reactive high-power impulse magnetron sputtering. The interlayer was deposited using negative bias voltages ranging between 100 and 900 V, and 1-fold or 3-fold substrate rotation. Scanning electron microscopy showed a dependence of coating morphology on substrate rotation. The N/Si ratio ranged from 1.10 to 1.25, as evaluated by X-ray photoelectron spectroscopy. Vertical scanning interferometry revealed that the coated, unpolished samples had a low average surface roughness between 16 and 33 nm. Rockwell indentations showed improved coating adhesion when a low bias voltage of 100 V was used to deposit the CrN interlayer. Wear tests performed in a reciprocating manner against Si3N4 balls showed specific wear rates lower than, or similar to that of CoCrMo. The study suggests that low negative bias voltages may contribute to a better performance of SiNx coatings in terms of adhesion. The low wear rates found in the current study support further development of silicon nitride-based coatings towards clinical application.