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Since the second half of the XX century, primer mixtures based on mercury fulminate have become a rare occurrence on small ammunition markets in Western Europe and North America. As a consequence, Hg-containing gunshot residue (GSR) particles have not been as deeply investigated as residues from lead-based primer mixtures. As a matter of fact, no mention of GSR particles from mercuric primers is made by the current ASTM standard procedure for gunshot residue analysis. However, those laboratories dealing with ammunition and firearms produced in Eastern Europe or Asia still have a forensic interest in Hg-containing GSR. In this paper, a brief description of chemical composition and inner morphology of GSR particles from three different mercuric primers is reported. Regarding composition, arguments are given to promote SbSnHg residues to Characteristic of GSR particles when mercuric primers are discharged. From a morphological point of view, presence of inner nodules and other inhomogeneities were shown in GSR particles milled in a FIB/SEM. Moreover, mercury vaporization under the electron beam was observed for a particle reduced to a lamella. Mercury evanescence in GSR was interpreted in terms of mercury segregation during particle formation and higher mobility of Hg atoms in presence of defects (vacancies) in a strained lattice., Competing Interests: Declaration of Competing Interest None., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In the field of encapsulation, microcapsules containing perfume have emerged as effective vehicles for delivering active ingredients across various applications. The present study employed a multivariate analysis framework to examine polyacrylate microcapsules for household products synthesized using different acrylate monomers. The advanced multivariate approach allowed us to quantify critical properties such as the Molecular Weight between Cross-links ( MW c ), mechanical attributes, Encapsulation Efficiency ( EE ), and On-Fabric delivery . It is worth noting that the mechanical properties were gauged using a novel nanoindentation technique, which measures the Rupture Force per unit diameter ( RFD ). Both Encapsulation Efficiency and On-Fabric delivery were assessed using GC-MS. Our findings identified the optimal microcapsule system as one synthesized with 100% aromatic hexafunctional urethane acrylate, showcasing a 94.3% Encapsulation Efficiency and an optimal RFD of 85 N/mm. This system achieved an exemplary On-Fabric delivery rate of 307.5 nmol/L. In summary, this research provides crucial insights for customizing microcapsule design to achieve peak delivery efficiency. Furthermore, by designing acrylic monomers appropriately, there is potential to reduce the amount of active ingredients used, owing to enhanced delivery efficiency and the optimization of other microcapsule properties. Such advancements pave the way for more environmentally friendly and sustainable production processes in the fast-moving consumer goods industry.

Surface free energy (SFE) of titanium surfaces plays a significant role in tissue engineering, as it affects the effectiveness and long-term stability of both active coatings and functionalization and the establishment of strong bonds to the newly growing bone. A new contact-mechanics methodology based on high-resolution non-destructive elastic contacting nanoindentation is applied here to study SFE of micro- and nano-structured titanium surfaces, right after their preparation and as a function of exposure to air. The effectiveness of different surface treatments in enhancing SFE is assessed. A time-dependent decay of SFE within a few hours is observed, with kinetics related to the sample preparation. The fast, non-destructive method adopted allowed for SFE measurements in very hydrophilic conditions, establishing a reliable comparison between surfaces with different properties.

In this work, the ternary titanium, copper, and silver (Ti-Cu-Ag) system is investigated as a potential candidate for the production of mechanically robust biomedical thin films. The coatings are produced by physical vapor deposition-magnetron sputtering (MS-PVD). The composite thin films are deposited on a silicon (100) substrate. The ratio between Ti and Cu was approximately kept one, with the variation of the Ag content between 10 and 35 at.%, while the power on the targets is changed during each deposition to get the desired Ag content. Thin film characterization is performed by X-ray diffraction (XRD), nanoindentation (modulus and hardness), to quantitatively evaluate the scratch adhesion, and atomic force microscopy to determine the surface topography. The residual stresses are measured by focused ion beam and digital image correlation method (FIB-DIC). The produced Ti-Cu-Ag thin films appear to be smooth, uniformly thick, and exhibit amorphous structure for the Ag contents lower than 25 at.%, with a transition to partially crystalline structure for higher Ag concentrations. The Ti-Cu control film shows higher values of 124.5 GPa and 7.85 GPa for modulus and hardness, respectively. There is a clear trend of continuous decrease in the modulus and hardness with the increase of Ag content, as lowest value of 105.5 GPa and 6 GPa for 35 at.% Ag containing thin films. In particular, a transition from the compressive (-36.5 MPa) to tensile residual stresses between 229 MPa and 288 MPa are observed with an increasing Ag content. The obtained results suggest that the Ag concentration should not exceed 25 at.%, in order to avoid an excessive reduction of the modulus and hardness with maintaining (at the same time) the potential for an increase of the antibacterial properties. In summary, Ti-Cu-Ag thin films shows characteristic mechanical properties that can be used to improve the properties of biomedical implants such as Ti-alloys and stainless steel.

This article reports the design, construction, and first use of an experimental device consisting of a specially designed vacuum chamber equipped with a reactive sputtering magnetron (RSM) to be used for controlled deposition of thin films on a Si(100) flat substrate. The setup was designed to allow for in situ and real-time recordings of X-ray diffraction patterns during the growth of the deposited films and was installed in the X-ray diffraction and spectroscopy beamline emerging from a superconducting wiggler source at the Brazilian Synchrotron Light Laboratory. The first use of the RSM setup was an in situ and real-time X-ray diffraction study of processes of growth of multilayered aluminum nitride thin films, whereas the operation parameters of the reactor were sequentially changed. This sequential process led to the development of multilayered films. Alternate variations in chamber pressure and magnetron power density allowed us to obtain thin films composed of several micrometer thick layers, with alternate amorphous and (10·0), (00·2), or (10·1) textured polycrystalline structures.

The present study investigated the influence of nanoscale residual stress depth gradients on the nano-mechanical behavior and adhesion energy of aluminium nitride (AlN) and Al/AlN sputtered thin films on a (100) silicon substrate. By using a focused ion beam (FIB) incremental ring-core method, the residual stress depth gradient was assessed in the films in comparison with standard curvature residual stress measurements. The adhesion energy was then quantified by using a nanoindentation-based model. Results showed that the addition of an aluminum layer gave rise to additional tensile stress at the coating/substrate interface, which can be explained in terms of the differences of thermal expansion coefficients with the silicon substrate. Therefore, the coatings without the Al layer showed better adhesion because of a more homogeneous compressive residual stress in comparison with the coating having the Al layer, even though both groups of coatings were produced under the same bias voltage. Results are discussed, and some general suggestions are made on the correlation between coating/substrate property combinations and the adhesion energy of multilayer stacks. The results suggested that the Al bond layer and inhomogeneous residual stresses negatively affected the adhesion of AlN to a substrate such as silicon.

The present work deals with a new technique to produce complex micro- and nano-scale patterns with high accuracy by FIB micro machining. The proposed method is related to the production of stream file, which is optimized through a software interface. A unique sampling approach is used to optimize the conversion from a 3D meshed CAD object to the focused ion beam (FIB) digital to analogue converter (DAC). The method uses a novel scan strategy, sensitive to the pattern local geometry and size, to define the optimal ion beam path, dwell time and the scanning pitch. This not only allows to minimize the redeposition but also to obtain accurate and scalable milling routines. In order to show the applicability of the method, a hemisphere and a pyramid shape are milled and compared to the shapes obtained using the conventional techniques. Results show that the method is very effective in producing complex shapes while overcoming the detrimental effect of conventional raster/serpentine FIB strategies, such as redeposition. Lastly, a fish-net structure with a pitch of ∼200nm as well as a series of truncated cones with sub-micrometrical details are realized to show the potential impact of this new method. Results show that a spatial resolution of less than 100nm is achievable with the help of this method., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Objectives: The production of fixed partial dentures (FPDs) induces complex residual stress profiles, due to both the thermal expansion coefficient mismatch between the veneering ceramic and the framework and to the thermal gradients occurring during the final cooling. Detailed knowledge of residual stress distributions in the veneering ceramics is important to understand the interface phenomena with the framework and the consequences of the different firing systems. The first objective of this study was to analyse the residual stress distribution in heat-pressed ceramic on zirconia core with micrometer spatial resolution, with also a focus on the stress at the interface versus porcelain-fused-to-metal samples. The second purpose was to correlate the residual stress with the fracture toughness., Methods: The micron-scale focused ion beam (FIB) ring-core method was used to map the residual stress over the cross-sections of the veneering ceramics. The methodology is based on FIB micro-milling of annular trenches, combined with high-resolution in situ scanning electron microscope (SEM) imaging, a full field strain analysis by digital image correlation (DIC) and numerical models for residual stress calculation. Fracture toughness was evaluated by using high load Vickers indentation and hardness/modulus were measured by nanoindentation testing also across the interfaces., Results: Both prosthetic systems showed a compressive stress at the ceramic surface on a micron-scale. The stress profile for porcelain fused to metal (PFM) showed a transition to tensile stress at the half of the layer, whilst the stress in proximity of the interface was more compressive in both the cases. Residual stress on a micron scale are higher in magnitude than the corresponding macro-scale values reported in the literature, due to the stress relaxation given, at larger scales, by micro-voids and cracks. The stress field was directly correlated with the indentation fracture toughness, which was higher in those areas where the compressive stress is greater. Stress analysis in correspondence of interfacial porosity for the zirconia sample also showed that micro-defects could induce local modifications of the residual stress field, which may even locally generate a tensile stress state., Significance: The interfacial stress in dental systems was analysed on a micron scale and can give further insights into the process/property/performance correlation for this class of materials. In particular, interfacial and/or local modifications of the residual stress are expected to have a significant influence on crack nucleation mechanism in correspondence of micro-defects. A direct correlation between residual stress distribution and fracture toughness was proposed. It is noteworthy that the method can be used to study real crowns and bridges. In fact, complex geometries can be easily analysed by this procedure., (Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Recently introduced FIB/SEM analysis in microscopy seems to provide a high-resolution characterization of the samples by 3D (FIB) cross-sectioning and (SEM) high resolution imaging. The aim of this study was to apply the FIB/SEM and SEM/EDS analysis to the interfaces of a metal-ceramic vs. two zirconia-ceramic systems. Plate samples of three different prosthetic systems were prepared in the dental lab following the manufacturers' instructions, where metal-ceramic was the result of a ceramic veneering (porcelain-fused-to-metal) and the two zirconia-ceramic systems were produced by the dedicated CAD-CAM procedures of the zirconia cores (both with final sintering) and then veneered by layered or heat pressed ceramics. In a FIB/SEM equipment (also called DualBeam), a thin layer of platinum (1 μm) was deposited on samples surface crossing the interfaces, in order to protect them during milling. Then, increasingly deeper trenches were milled by a focused ion beam, first using a relatively higher and later using a lower ion current (from 9 nA to 0.28 nA, 30KV). Finally, FEG-SEM (5KV) micrographs (1000-50,000X) were acquired. In a SEM the analysis of the morphology and internal microstructure was performed by 13KV secondary and backscattered electrons signals (in all the samples). The compositional maps were then performed by EDS probe only in the metal-ceramic system (20kV). Despite the presence of many voids in all the ceramic layers, it was possible to identify: (1) the grain structures of the metallic and zirconia substrates, (2) the thin oxide layer at the metal-ceramic interface and its interactions with the first ceramic layer (wash technique), (3) the roughness of the two different zirconia cores and their interactions with the ceramic interface, where the presence of zirconia grains in the ceramic layer was reported in two system possibly due to sandblasting before ceramic firing.

The depth profile of thin film layers on bulk substrate, avoiding the cross-sectioning of samples, is commonly performed by techniques such as X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectroscopy (SIMS). Techniques based on X-ray emission intensity measurements by energy dispersive spectroscopy (EDS), with conventional matrix or ZAF correction, are normally applied to cross-sectioned samples. This article compares XPS with surface X-ray intensity measurements by EDS, carried out with a more realistic X-ray generation and absorption model, known as the pi(rho Z) model. The pi(rho Z) approach has been adopted together with Monte Carlo simulation for the proper selection of SEM accelerating voltages, in conjunction with the analysis of SEM morphological images for thin film density correction. The method discussed hereafter and compared with the XPS technique, has advantages of higher lateral resolution, non-destructive elemental analyses, morphological visualization, low cost, and faster performance. This methodology has been followed to verify the layered structure of SnO2/metal-based gas sensors. X-ray intensities were measured using an EDS ultra-thin window detector. Two different porous layers, 25-nm thick of SnO2 and 10-nm thick of Cu, were detected, showing better agreement with their nominal thickness compared to results obtained using XPS measurements where porosity affects XPS data. If confirmed to be reliable and as effective as XPS depth profiling, this technique may be adopted for process quality control purposes.