Europium sulfide (EuS) thin films are appealing as ferromagnetic semiconductors and luminescent and optomagnetic materials owing to their unique functional properties. With the emerging field of ...spintronics and magneto-optical devices, chemical vapor deposition (CVD) offers a versatile platform to tune the material properties and the method to fabricate device structures needed for such applications. Herein, we report the growth of high-quality cubic EuS via a versatile CVD process where the new Eu(III) precursors employed facilitate the formation of the target EuS layers under moderated process conditions. Based on the prior evaluation of the physicochemical properties of these precursors using thermal analysis and density functional theory studies, adequate volatility, thermal stability, and sufficient reactivity toward potential co-reactants, namely, elemental sulfur, could be inferred. Thus, the use of toxic hydrogen sulfide generally needed for sulfide film depositions could be avoided, which is a significant advantage in terms of simplifying the deposition process. The as-deposited thin films were analyzed in terms of the structure, composition, and morphology, revealing highly oriented polycrystalline and stoichiometric EuS films. UV/vis measurements yielded a band gap of around 1.6 eV, and Raman spectroscopy exhibited a coupling between the phonons and electron spin systems of EuS. These findings, together with the soft ferromagnetic character of the films derived from semiconducting quantum interference device measurements, signify the potential of CVD-grown EuS for future technological applications.
Vibrational spectroscopy can detect characteristic biomolecular signatures and thus has the potential to support diagnostics. Fabry disease (FD) is a lipid disorder disease that leads to ...accumulations of globotriaosylceramide in different organs, including the heart, which is particularly critical for the patient's prognosis. Effective treatment options are available if initiated at early disease stages, but many patients are late- or under-diagnosed. Since Coherent anti-Stokes Raman (CARS) imaging has a high sensitivity for lipid/protein shifts, we applied CARS as a diagnostic tool to assess cardiac FD manifestation in an FD mouse model. CARS measurements combined with multivariate data analysis, including image preprocessing followed by image clustering and data-driven modeling, allowed for differentiation between FD and control groups. Indeed, CARS identified shifts of lipid/protein content between the two groups in cardiac tissue visually and by subsequent automated bioinformatic discrimination with a mean sensitivity of 90-96%. Of note, this genotype differentiation was successful at a very early time point during disease development when only kidneys are visibly affected by globotriaosylceramide depositions. Altogether, the sensitivity of CARS combined with multivariate analysis allows reliable diagnostic support of early FD organ manifestation and may thus improve diagnosis, prognosis, and possibly therapeutic monitoring of FD.
Amorphous carbon (a-C) attracts great attention in tribology research and thin film technologies due to its versatile properties. However, high temperatures and mechanical stresses may cause ...significant changes in the structural ordering of the a-C network. We present an optical method to initiate structural ordering and to probe solid-to-solid structural transitions of element modified a-C films. A pulsed pump laser introduces heat into the film in a controlled manner, while a second laser probes confocally the first- and second-order Raman scattering signatures of the a-C network. For low pump power, the number of defects and non-sixfold aromatic rings is reduced. A further increase in the laser power leads to sharply evolved changes in the Raman scattering features, indicating a transition from a-C to defected graphite and an effusion of hydrogen. Moreover, graphite-dominant defect relaxation and an enhancement in hexagonal lattice areas occur and, in turn, activate second-order Raman scattering lines. A rising laser power subsequently results in progressive graphitization. Chemical modification of the films with Si or Cu enhances their thermal stability and even shifts the upper thermal limit of the film ablation, while the a-C:W film demonstrates a more efficient enrichment of nanocrystalline graphitic clusters.
Modular artificial hip joints are a clinical standard today. However, the release of wear products from the head-taper interface, which includes wear particles in the nm size range, as well as metal ...ions, have raised concerns. Depending on the loading of such taper joints, a wide variety of different mechanisms have been found by retrieval analyses. From these, this paper concentrates on analyzing the contribution of gross slip fretting corrosion at ultra-mild wear rates using a bovine calf serum solution (BCS) as the lubricant. The parameters were chosen based on biomechanical considerations, producing wear rates of some ng/m wear path. In parallel, the evolution of tribomaterial (third bodies) was analyzed as to its constituents and generation rates. It has already been shown earlier that, by an advantageous combination of wear mechanisms and submechanisms, certain constituents of the tribomaterial remain inside the contact area and act like extreme-pressure lubricant additives. For the known wear and corrosion resistance of austenitic high-nitrogen steels (AHNSs), which outperform CoCrMo alloys even under inflammatory conditions, we hypothesized that such steels will generate ultra-mild wear rates under gross slip fretting. While testing AHNSs against commercially available biomedical-grade materials of CoCrMo and TiAlV alloys, as well as zirconia-toughened alumina (ZTA) and against itself, it was found that AHNSs in combination with a Ti6Al4V alloy generated the smallest wear rate under gross slip fretting corrosion. This paper then discusses the wear behavior on the basis of ex situ analyses of the worn surfaces as to the acting wear mechanisms and submechanisms, as well as to the tribological reaction products.
•The structure of a-C:X in a-C/a-C:X is not affected by the multilayer design.•a-C/a-C:X structures reveal a higher hardness than a-C:X monolayers.•a-C/a-C:Si shows a low friction as a-C:Si, but with ...significantly lower wear.•a-C/a-C:W has a similar wear rate as a-C:W, but exhibits a lower friction.•The multilayer design is beneficial in exploiting advantageous properties of a-C:X.
Designing the film architecture of amorphous carbon based systems is effective in tailoring the tribo-mechanical properties. For this purpose, alternating a-C and a-C:X layers, with X = Si or W, were grown with a layer ratio of 1, a bilayer period of ~200 nm, and a bilayers number of 5 in a magnetron sputtering process. By comparing with a-C(:X) monolayers, the structure and tribo-mechanical properties of alternating a-C/a-C:X films were evaluated.
Although the bonding state of the a-C network of a-C:X in a-C/a-C:X is comparable to monolayered a-C:X, the multilayer design significantly affects the tribo-mechanical properties. The a-C/a-C:X multilayers exhibit a higher hardness compared to a-C:X. With a coefficient of friction of 0.12 ± 0.01, a-C/a-C:Si shows a low friction as a-C:Si with 0.09 ± 0.01, but the wear rate is significantly lower for a-C/a-C:Si with (3.4 ± 0.7) × 10-7 mm³/Nm than a-C:Si with (8.3 ± 1.0) × 10-7 mm³/Nm. Contrarily, a-C/a-C:W and a-C:W provide similar wear rates of 1.2 to 1.4 × 10-7 mm³/Nm, but the coefficient of friction is lower for a-C/a-C:W with 0.29 ± 0.02 than a-C:W with 0.36 ± 0.01. Hence, the multilayer design is efficient in improving the tribo-mechanical properties of a-C:X based films.
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Understanding the generation of third body particles and their contribution to the formation of tribofilms of MoSx thin films is still challenging due to a large number of influencing factors. ...Besides the structure of the as-deposited MoSx films, the environment and the conditions during the Ball-on-disk tests affect tribofilms and thus the friction. Therefore, the influence of the surface pressure and sliding velocity in air, argon and nitrogen environments on the generation of the third body particles and the tribofilm formation of randomly oriented MoSx films is investigated. A high surface pressure is one major factor to achieve low friction, especially under humid conditions, which is important considering the use in industrial applications, for example dry-running screw machines. However, the mechanisms leading to that frictional behavior are still affected by the surrounding environment. While low friction is caused by a more extensive tribofilm formation in air, in argon and nitrogen, large size third body particles dispensed all over the contact area contribute to a lower friction. Raman scattering reveal a different chemistry of these particles reflected in the absence of laser- or temperature-induced surface oxidation compared to the as-deposited film and the wear track. The Raman scattering results are discussed with respect to the wear particle size, its chemical reactivity and strain-induced bonding changes.
The Design of Experiments is a promising method to investigate the cause-effect relation between the mid-frequency magnetron sputtering parameters on the structural and mechanical properties of ...amorphous carbon (a-C) films. Based on the Central Composite Design, the cathode power of two graphite targets, bias voltage, and mid-frequency were simultaneously varied from 1500 to 4000 W, −100 to −200 V, and 20 to 50 kHz, respectively. The chemical bonding state was characterized using UV and visible Raman spectroscopy with excitation wavelengths of 266 and 532 nm. Corresponding measurements were performed by X-ray photoelectron spectroscopy (XPS) using synchrotron radiation. Additionally, hardness and elastic modulus of the sputtered a-C films were determined in nanoindentation tests.
Multi-wavelength Raman spectroscopy identified an sp3 content below 20%, with most a-C films having an sp3 value in the range of 12 to 18%. The formation of sp3 bonded atoms is negatively influenced by a high cathode power and bias voltage, whereas the highest sp3 content is obtained with a-C films sputtered with a cathode power and bias voltage of 2750 W and −150 V. However, higher values of the cathode power and bias voltage result in a film delamination and decrease of the sp3 concentration. The bonding state affects the mechanical properties, as high hardness and elastic modulus result from a high sp3 content. Therefore, a targeted adjustment of cathode power and bias voltage is necessary to obtain a-C films with a high hardness. In contrast, the mid-frequency does not have a significant impact on the mechanical properties. In conclusion, the Central Composite Design has proven to be a suitable method to investigate the cause-effects of the sputtering parameters on the properties of the a-C film.
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•Central Composite Design used to sputter a-C films and evaluate effects.•Evaluation of sp3 content with Raman scattering in UV and visible spectral range.•Targeted adjustment of cathode power and bias voltage favors high hardness.•Highest hardness of 24.9 ± 1.1 GPa and highest sp3 content of 20% obtained.
The deposition of ternary nitrides with the incorporation of carbon atoms into its structure has demonstrated to be a promising approach in the pursuit of wear-resistant and self-lubricating ...coatings. Firstly, both TiAlN and TiAlCN monolayers were deposited using direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS) onto quenched and tempered AISI H11 tool steel to be used as references. Acetylene was used as a carbon precursor, producing DCMS and HiPIMS TiAlCN coatings with 9.0 and 21.7 at.% C, respectively.
Subsequently, TiAlN/TiAlCN multilayers of various designs were also developed as follows: 5×10/500, 5×50/500 and 5×100/500 nm. Residual stresses of the coating systems were determined by X-ray radiation utilising an ETA-diffractometer with a Cu-Kα radiation source applying the sin2ψ method. Additionally, residual stresses depth gradients of the substrate before and after the deposition of the coatings were determined in a LEDDI 8-circle diffractometer equipped with a W-X-ray tube and operated in the energy-dispersive mode of diffraction. Great reduction of the compressive residual stresses in the coatings was observed after the introduction of carbon into the TiAlN coating structure, shifting from −1047 ± 149 to −307 ± 211 MPa for the DCMS and from −7035 ± 1361 to +989 ± 187 MPa for the HiPIMS coatings. In the multilayer coatings, compressive residual stresses increase along with the increment of the TiAlN interlayer. Additionally, residual stresses of the substrate in the near-surface are dragged from low compressive stresses (−218 ± 61) to tensile stresses in the range of 1000 to 2000 MPa for all the DCMS/substrate systems, a behaviour only presented in HiPIMS by the TiAlN monolayer. Wear coefficients of all the evaluated HiPIMS systems are notoriously lower than their DCMS counterparts. Compared to TiAlN, TiAlCN HiPIMS presented a lower coefficient of friction but a higher wear coefficient, which in turn was not reduced by the introduction of the multilayer systems. Finally, Scratch test and Rockwell C adhesion tests have shown higher adhesion of DCMS coatings than HiPIMS coatings, and a detriment of the monolayers adhesion by the implementation of TiAlN/TiAlCN multilayer systems. The understanding of the residual stresses, both in the coating and in the substrate, and the way they affect the tribomechanical performance of the system coating/substrate continues to be of great importance, especially for coatings deposited by new technologies such as HiPIMS and self-lubricating coatings.
•Great reduction of compressive residual stresses with the carbon inclusion in TiAlN.•High superficial residual stresses on the substrate after DCMS deposition.•Adhesion of DCMS coatings systems to AISI H11 is always higher than HiPIMS.•Ceramic/ceramic multilayer designs did not improved adhesion or wear.
•Laser-synthesized hard ceramic particles tested for high-pressure applications.•Huge potential of nano- and submicrometer spheres as additives in lubricants.•High impact of particle size and ...morphology on wear and fatigue failure on the tooth flank.
The lubricant is a central element in the transmission design. It primarily separates the two contact partners through a pressure-induced solidification in the lubrication gap, thus enabling the operation of heavily loaded sliding-rolling contacts. On the one hand, the quality and properties of a lubricant depend on the base oils, which differ by their viscosity and process-technological parameters. The addition of particulate additives gives the lubricants further functional properties that are not contained in the base oil. In this study, the influence of laser-synthesized yttria-stabilized zirconia nano- or submicrometer spheres as dispersed functional elements in the lubricant is studied, and their impact on wear and fatigue on the tooth flank is investigated. The work includes systematic investigations on the influence of the particle’s shape and size by running tests on a FZG gear test rig. Finally, the potential of the laser-generated particles as a lubricant additive is evaluated in a first conclusion.
For tribological applications, adding Si or W to hydrogen-free a-C or hydrogenated a-C:H is highly beneficial to tailor the film properties. Hence, a direct comparison between Si- and W-containing ...a-C and a-C:H considerably enhances the understanding of both the interaction between Si or W and the hydrogenation state as well as its effect on the structure and tribo-mechanical properties of these films. Therefore, non-modified a-C(:H), Si-containing a-C(:H):Si, and W-containing a-C(:H):W films were systematically grown in a mid-frequency magnetron sputtering process.
The formation of W-based nanocrystallites within a-C(:H):W is identified by x-ray diffraction, whereas a-C(:H):Si still possesses an amorphous character. Raman scattering spectra show higher I(D)/I(G) ratios for hydrogen-free a-C(:X) films compared to the respective a-C(:H):X, indicating a higher number and larger sizes of sp2 clusters in the carbon network. For the hydrogenated a-C:H:X films, the reduced number of sp2 clusters is related to the presence of terminating CH bonds, which were detected as stretching modes. Among the different films, a-C:W has the highest I(D)/I(G) ratio, while a-C:H and a-C:H:Si exhibit the lowest I(D)/I(G) values. While a-C:Si and a-C:H:Si are characterized by comparable hardness values of (18.7 ± 1.3) and (18.4 ± 1.1) GPa, a-C:W has a lower hardness of (13.8 ± 1.0) GPa compared to a-C:H:W with (17.5 ± 0.9) GPa. Among all modified a-C(:H):X films, a-C:Si and a-C:H:Si reveal the lowest coefficients of friction, but show highest wear rates in dry sliding against 100Cr6 steel. Contrarily, a-C:W has higher friction and wear than a-C:H:W. Consequently, the Si-containing a-C(:H):Si films demonstrate comparable tribo-mechanical properties, while the hydrogenation state leads to different tribo-mechanical properties of a-C(:H):W.
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•a-C:W undergoes a structural change from amorphous to crystalline.•a-C:H:Si exhibits the highest I(D)/I(G) ratio, indicating the highest amount of sp3 bonds•A modification with tungsten promotes the formation of sp2 bonds•Silicon-modified films reveal the lowest coefficient of friction with μ = 0.086 ± 0.018 for a-C:Si against 100Cr6.
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