Structural segregation in GSR from mercuric primers. A preliminary study.

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.

A Methodology for Multivariate Investigation on the Effect of Acrylate Molecular Structure on the Mechanical Properties and Delivery Efficiency of Microcapsules via In Situ Polymerization.

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 (MWc), 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.

Influence of the Silver Content on Mechanical Properties of Ti-Cu-Ag Thin Films.

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.

A Nanoindentation Approach for Time-Dependent Evaluation of Surface Free Energy in Micro- and Nano-Structured Titanium.

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.

Effects of Residual Stress Distribution on Interfacial Adhesion of Magnetron Sputtered AlN and AlN/Al Nanostructured Coatings on a (100) Silicon Substrate.

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.

A method to improve the quality of 2.5 dimensional micro-and nano-structures produced by focused ion beam machining.

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.

Verification of Layered Structures in SnO2/Metal-based Gas Sensors by X-ray Microanalysis: Comparison with X-ray Photoelectron Spectroscopy.

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.