Susann Schmidt

Mechanical and tribological behavior of silicon nitride and silicon carbon nitride coatings for total joint replacements

Total joint replacements currently have relatively high success rates at 10-15 years; however, increasing ageing and an active population places higher demands on the longevity of the implants. A wear resistant configuration with wear particles that resorb in vivo can potentially increase the lifetime of an implant. In this study, silicon nitride (SixNy) and silicon carbon nitride (SixCyNz) coatings were produced for this purpose using reactive high power impulse magnetron sputtering (HiPIMS). The coatings are intended for hard bearing surfaces on implants. Hardness and elastic modulus of the coatings were evaluated by nanoindentation, cohesive, and adhesive properties were assessed by micro-scratching and the tribological performance was investigated in a ball-on-disc setup run in a serum solution. The majority of the SixNy coatings showed a hardness close to that of sintered silicon nitride (~18 GPa), and an elastic modulus close to that of cobalt chromium (~200 GPa). Furthermore, all except one of the SixNy coatings offered a wear resistance similar to that of bulk silicon nitride and significantly higher than that of cobalt chromium. In contrast, the SixCyNz coatings did not show as high level of wear resistance.

Ion mass spectrometry investigations of the discharge during reactive high power pulsed and direct current magnetron sputtering of carbon in Ar and Ar/N2

Ion mass spectrometry was used to investigate discharges formed during high power impulse magnetron sputtering (HiPIMS) and direct current magnetron sputtering (DCMS) of a graphite target in Ar and ...

Influence of inert gases on the reactive high power pulsed magnetron sputtering process of carbon-nitride thin films

The influence of inert gases (Ne, Ar, Kr) on the sputter process of carbon and carbon-nitride (CNx) thin films was studied using reactive high power pulsed magnetron sputtering (HiPIMS). Thin solid films were synthesized in an industrial deposition chamber from a graphite target. The peak target current during HiPIMS processing was found to decrease with increasing inert gas mass. Time averaged and time resolved ion mass spectroscopy showed that the addition of nitrogen, as reactive gas, resulted in less energetic ion species for processes employing Ne, whereas the opposite was noticed when Ar or Kr were employed as inert gas. Processes in nonreactive ambient showed generally lower total ion fluxes for the three different inert gases. As soon as N2 was introduced into the process, the deposition rates for Ne and Ar-containing processes increased significantly. The reactive Kr-process, in contrast, showed slightly lower deposition rates than the nonreactive. The resulting thin films were characterized rega...

Low-temperature growth of low friction wear-resistant amorphous carbon nitride thin films by mid-frequency, high power impulse, and direct current magnetron sputtering

The potential of different magnetron sputtering techniques for the synthesis of low friction and wear resistant amorphous carbon nitride (a-CNx) thin films onto temperature-sensitive AISI52100 bearing steel, but also Si(001) substrates was studied. Hence, a substrate temperature of 150 °C was chosen for the film synthesis. The a-CNx films were deposited using mid-frequency magnetron sputtering (MFMS) with an MF bias voltage, high power impulse magnetron sputtering (HiPIMS) with a synchronized HiPIMS bias voltage, and direct current magnetron sputtering (DCMS) with a DC bias voltage. The films were deposited using a N2/Ar flow ratio of 0.16 at the total pressure of 400 mPa. The negative bias voltage, Vs, was varied from 20 to 120 V in each of the three deposition modes. The microstructure of the films was characterized by high-resolution transmission electron microscopy and selected area electron diffraction, while the film morphology was investigated by scanning electron microscopy. All films possessed an amorphous microstructure, while the film morphology changed with the bias voltage. Layers grown applying the lowest substrate bias of 20 V exhibited pronounced intercolumnar porosity, independent of the sputter technique. Voids closed and dense films are formed at Vs ≥ 60 V, Vs ≥ 100 V, and Vs = 120 V for MFMS, DCMS, and HiPIMS, respectively. X-ray photoelectron spectroscopy revealed that the nitrogen-to-carbon ratio, N/C, of the films ranged between 0.2 and 0.24. Elastic recoil detection analysis showed that Ar content varied between 0 and 0.8 at. % and increased as a function of Vs for all deposition techniques. All films exhibited compressive residual stress, σ, which depends on the growth method; HiPIMS produces the least stressed films with values ranging between −0.4 and −1.2 GPa for all Vs, while CNx films deposited by MFMS showed residual stresses up to −4.2 GPa. Nanoindentation showed a significant increase in film hardness and reduced elastic modulus with increasing Vs for all techniques. The harder films were produced by MFMS with hardness as high as 25 GPa. Low friction coefficients, between 0.05 and 0.06, were recorded for all films. Furthermore, CNx films produced by MFMS and DCMS at Vs = 100 and 120 V presented a high wear resistance with wear coefficients of k ≤ 2.3 × 10−5 mm3/Nm. While all CNx films exhibit low friction, wear depends strongly on the structural and mechanical characteristics of the films. The MFMS mode is best suited for the production of hard CNx films, although high compressive stresses challenge the application on steel substrates. Films grown in HiPIMS mode provide adequate adhesion due to low residual stress values, at the expense of lower film hardness. Thus, a relatively wide mechanical property envelope is presented for CNx films, which is relevant for the optimization of CNx film properties intended to be applied as low friction and wear resistant coatings.The potential of different magnetron sputtering techniques for the synthesis of low friction and wear resistant amorphous carbon nitride (a-CNx) thin films onto temperature-sensitive AISI52100 bearing steel, but also Si(001) substrates was studied. Hence, a substrate temperature of 150 °C was chosen for the film synthesis. The a-CNx films were deposited using mid-frequency magnetron sputtering (MFMS) with an MF bias voltage, high power impulse magnetron sputtering (HiPIMS) with a synchronized HiPIMS bias voltage, and direct current magnetron sputtering (DCMS) with a DC bias voltage. The films were deposited using a N2/Ar flow ratio of 0.16 at the total pressure of 400 mPa. The negative bias voltage, Vs, was varied from 20 to 120 V in each of the three deposition modes. The microstructure of the films was characterized by high-resolution transmission electron microscopy and selected area electron diffraction, while the film morphology was investigated by scanning electron microscopy. All films possessed an...

Dissolution behaviour of silicon nitride coatings for joint replacements

In this study, the dissolution rate of SiNx coatings was investigated as a function of coating composition, in comparison to a cobalt chromium molybdenum alloy (CoCrMo) reference. SiNx coatings with N/Si ratios of 0.3, 0.8 and 1.1 were investigated. Electrochemical measurements were complemented with solution (inductively coupled plasma techniques) and surface analysis (vertical scanning interferometry and x-ray photoelectron spectroscopy). The dissolution rate of the SiNx coatings was evaluated to 0.2-1.4 nm/day, with a trend of lower dissolution rate with higher N/Si atomic ratio in the coating. The dissolution rates of the coatings were similar to or lower than that of CoCrMo (0.7-1.2 nm/day). The highest nitrogen containing coating showed mainly Si-N bonds in the bulk as well as at the surface and in the dissolution area. The lower nitrogen containing coatings showed Si-N and/or Si-Si bonds in the bulk and an increased formation of Si-O bonds at the surface as well as in the dissolution area. The SiNx coatings reduced the metal ion release from the substrate. The possibility to tune the dissolution rate and the ability to prevent release of metal ions encourage further studies on SiNx coatings for joint replacements.

First measurements with new high-resolution gadolinium-GEM neutron detectors

European Spallation Source instruments like the macromolecular diffractometer (NMX) require an excellent neutron detection efficiency, high-rate capabilities, time resolution, and an unprecedented spatial resolution in the order of a few hundred micrometers over a wide angular range of the incoming neutrons. For these instruments solid converters in combination with Micro Pattern Gaseous Detectors (MPGDs) are a promising option. A GEM detector with gadolinium converter was tested on a cold neutron beam at the IFE research reactor in Norway. The μTPC analysis, proven to improve the spatial resolution in the case of 10B converters, is extended to gadolinium based detectors. For the first time, a Gd-GEM was successfully operated to detect neutrons with a measured efficiency of 11.8% at a wavelength of 2 Aand a position resolution better than 250 μm.

The Multi-Blade Boron-10-based neutron detector for high intensity neutron reflectometry at ESS

The Multi-Blade is a Boron-10-based gaseous detector introduced to face the challenge arising in neutron reflectometry at pulsed neutron sources. Neutron reflectometers are the most challenging instruments in terms of instantaneous counting rate and spatial resolution. This detector has been designed to cope with the requirements set for the reflectometers at the upcoming European Spallation Source (ESS) in Sweden. Based on previous results obtained at the Institut Laue-Langevin (ILL) in France, an improved demonstrator has been built at ESS and tested at the Budapest Neutron Centre (BNC) in Hungary and at the Source Testing Facility (STF) at the Lund University in Sweden. A detailed description of the detector and the results of the tests are discussed in this manuscript.

SiNx Coatings Deposited by Reactive High Power Impulse Magnetron Sputtering: Process Parameters Influencing the Nitrogen Content

Reactive high power impulse magnetron sputtering (rHiPIMS) was used to deposit silicon nitride (SiNx) coatings for biomedical applications. The SiNx growth and plasma characterization were conducted in an industrial coater, using Si targets and N2 as reactive gas. The effects of different N2-to-Ar flow ratios between 0 and 0.3, pulse frequencies, target power settings, and substrate temperatures on the discharge and the N content of SiNx coatings were investigated. Plasma ion mass spectrometry shows high amounts of ionized isotopes during the initial part of the pulse for discharges with low N2-to-Ar flow ratios of <0.16, while signals from ionized molecules rise with the N2-to-Ar flow ratio at the pulse end and during pulse-off times. Langmuir probe measurements show electron temperatures of 2-3 eV for nonreactive discharges and 5.0-6.6 eV for discharges in transition mode. The SiNx coatings were characterized with respect to their composition, chemical bond structure, density, and mechanical properties by X-ray photoelectron spectroscopy, X-ray reflectivity, X-ray diffraction, and nanoindentation, respectively. The SiNx deposition processes and coating properties are mainly influenced by the N2-to-Ar flow ratio and thus by the N content in the SiNx films and to a lower extent by the HiPIMS frequencies and power settings as well as substrate temperatures. Increasing N2-to-Ar flow ratios lead to decreasing growth rates, while the N content, coating densities, residual stresses, and the hardness increase. These experimental findings were corroborated by density functional theory calculations of precursor species present during rHiPIMS.

Silicon oxynitride films deposited by reactive high power impulse magnetron sputtering using nitrous oxide as a single-source precursor

Silicon oxynitride thin films were synthesized by reactive high power impulse magnetron sputtering of silicon in argon/nitrous oxide plasmas. Nitrous oxide was employed as a single-source precursor ...

Tuning the Emission Energy of Chemically Doped Graphene Quantum Dots

Tuning the emission energy of graphene quantum dots (GQDs) and understanding the reason of tunability is essential for the GOD function in optoelectronic devices. Besides material-based challenges, the way to realize chemical doping and band gap tuning also pose a serious challenge. In this study, we tuned the emission energy of GQDs by substitutional doping using chlorine, nitrogen, boron, sodium, and potassium dopants in solution form. Photoluminescence data obtained from (Cl- and N-doped) GQDs and (B-, Na-, and K-doped) GQDs, respectively exhibited red- and blue-shift with respect to the photoluminescence of the undoped GQDs. X-ray photoemission spectroscopy (XPS) revealed that oxygen functional groups were attached to GQDs. We qualitatively correlate red-shift of the photoluminescence with the oxygen functional groups using literature references which demonstrates that more oxygen containing groups leads to the formation of more defect states and is the reason of observed red-shift of luminescence in GQDs. Further on, time resolved photoluminescence measurements of Cl- and N-GQDs demonstrated that Cl substitution in GQDs has effective role in radiative transition whereas in N-GQDs leads to photoluminescence (PL) quenching with non-radiative transition to ground state. Presumably oxidation or reduction processes cause a change of effective size and the bandgap.