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The production of ammonia (NH 3 ) with low-pressure, radiofrequency plasmas is studied in this paper in a wide range of experimental conditions using tungsten as a catalyst. The relative position of the tungsten foil in the pyrex tube was observed to dramatically impact ammonia formation. By positioning the catalyst in the middle of the tube, the concentration of NH 3 peaked at 120 W with ≈20 mol %, while it decreased by more than a factor of 2 at 300 W. When the foil was placed close to the end of the tube, the production of NH 3 was rather stable beyond 120 W. These results provide clear evidence of the surface's role in the local enhancement of the NH 3 formation rates. In the plasma volume, at some distance from the foil, the decomposition of NH 3 is the major occurring process and the decomposition rate increases with the power primarily due to a higher electron density. The optimum production of NH 3 was found to be at 45 mol % N 2 and 120 W, and the position of the maximum was observed to slightly decrease to

In ITER, the first mirrors would be vulnerable to deposition from the first wall materials, namely beryllium (Be) and tungsten (W) in mixed compositions. In this study we investigate the capactively coupled RF plasma sputtering of such mixed Be-W deposits on rhodium-coated substrates, using deuterium as the process gas, and track the enrichment of W during the sputtering process. Experiments were conducted on Be-W deposits with W concentration varying from 2 to 8.3 at.%, and maximal deuterium ion energies in the plasma of 70 and 220 eV. The evolution of the W concentration in the deposits during the plasma sputtering depended considerably on both deuterium ion energy as well as the initial concentration of W in the films. With 220 eV sputtering, a rapid enrichment of W was observed, with all the W changing from BeW before sputtering to metallic W and its oxides after sputtering. With 70 eV sputtering, there was no net change in the W concentration, as long as the initial concentration of W in the film was below 4 at.%. Moreover, the W remained considerably in the state of BeW after the sputtering as well. However, a W enrichment was also observed with 70 eV sputtering, when the W concentration in the films was higher (8.3 at.%). The rate of W enrichment was also observed to increase monotonically with the increase in the initial concentration of W in the deposits. SDTrimSP simulations performed with experimental parameters indicate that sputtering yield of Be increases with W concentrations in the Be-W layers due to backscattering of D projectiles off W atoms. These studies show that low energy deuterium sputtering of mixed Be-W layers with low W concentrations, allows for removal of Be without rapidly enriching W in the films, making it a promising option for ITER.

The first mirror (FM) cleaning operations in ITER are expected to be executed in the presence of a ∼ 3 T magnetic field. In the RF plasma cleaning configuration, this would have a significant influence on the plasma properties, ion energy, angle of incidence as well as flux spatial distribution. To this end, RF discharges were excited in an ITER-sized mock-up of a first mirror unit (FMU) consisting of a powered first mirror M1 and a grounded second mirror M2 placed in a homogeneous 3 T magnetic field. The plasma discharge was confined in a beam extending in the direction of the magnetic field, consequently wetting a limited portion of the FMU walls. In the DC-decoupled scheme (without λ/4 filter), this considerably influenced the self-bias voltage V DC that develops on M1. Changing the angle α between M1 normal and magnetic field, modified the plasma wetted wall area A g and the resulting V DC varied by over two orders of magnitude. Plasma exposure experiments were also done in the DC-coupled scheme (with λ/4 filter), wherein the angle and wetted surface determined the area of wall sputtered. Increasing α led to an increase in the sputtered wall area A g, and consequently the wall deposition on grounded M2. However, in all the cases M1 was entirely clean with the exception of edge deposits in some. In contrast, both M1 and M2 are coated with wall deposits in the absence of a magnetic field and a similar plasma exposure. The results show that plasma cleaning with λ/4 filter in a 3 T magnetic field at ITER could potentially prevent the parasitic wall deposition on FMs. The results also highlight the importance of FM orientation in the magnetic field and the wetted area in the plasma cleaning in both the DC-coupled and decoupled schemes within the ITER diagnostic systems.

We present an experimental investigation of the ion flux–energy distribution functions (IFEDFs) obtained across grounded grids in an asymmetric capacitively coupled RF source using a helium discharge. The powered electrode in the RF source is DC-grounded via a λ/4 filter, which lifts its DC potential to zero. Grids of different dimensions (hole width, thickness, and geometric transparency) were used to confine the plasma, while the IFEDF of the ion beam departing the grid and reaching the reactor walls was studied using a retarding field energy analyser. The IFEDF obtained was double-peaked, indicating the presence of fast ions arriving from the plasma source, and cold ions generated upon charge exchange collisions between the fast ions and neutrals. The flux, as well as the peak energies of the two ion groups, depended significantly on the process parameters: RF power, He pressure, the distance between grids and walls, and the dimensions of the grids. The results indicate that confining plasma with grids can reduce the ion flux at the walls by over 60%, significantly lowering the wall sputtering rate. This was confirmed with a dedicated long-exposure plasma discharge with a gridded plasma reactor, wherein less than 1 nm of Cu deposition was found on the DC-grounded powered electrode, and the surface reflectivity was preserved to pristine values. In contrast, a similar experiment in a gridless reactor resulted in Cu deposition of 35 nm with a drastic drop in surface reflectivity. These studies are of great importance for the application of similar RF plasma sources with in-situ cleaning of diagnostic mirrors in fusion devices, as well as in a variety of plasma processing applications.

The fusion reactor ITER will use nitrogen gas to spread the power loads on the tungsten (W) divertor, which extracts heat and ash produced by the fusion reaction. However, once ionised in the fusion plasma, the nitrogen ions and radicals will form stable compounds with the fusion fuel i.e. hydrogen isotopes deuterium (D) and tritium (T). As a result, ammonia isotopologues (e.g., ND 2 T) will be formed. As a polar molecule, ammonia will stick on the reactor walls, imposing concerns on the tritium safety limit for ITER 1 . Hence, it is crucial to investigate the conditions at which ammonia is produced and identify strategies to destroy/process it.

Plasma catalysis has drawn attention in the past few decades as a possible alternative to the Haber-Bosch process for ammonia production. In particular, radio frequency plasma assisted catalysis has the advantage of its adaptability to the industrial scale. However, in the past years, very few experimental studies have focused on the synthesis of ammonia from nitrogen/hydrogen radio frequency plasma. As a consequence, to date, there has been little agreement about the complex mechanisms underlying the radio frequency plasma-catalyst interactions. Gaining such an understanding is therefore essential for exploiting the potential of radio frequency plasma catalysis for ammonia production. In this study, we present results of ammonia formation from a nitrogen/hydrogen radio frequency plasma both without and with a tungsten catalyst for different initial nitrogen ratios. High yields of ammonia up to 32% at 25/75% of nitrogen/hydrogen were obtained using a combination of radio frequency low pressure plasma and a W surface as a catalyst. Furthermore, based on chemical analysis of the catalytic surface composition, a formation pathway of ammonia via the Eley-Rideal mechanism between adsorbed nitrogen and hydrogen from the gas phase is presented.

Background: It is hypothesised that simulation enhances progression along the initial phase of the surgical learning curve. Objective: To evaluate whether residents undergoing additional simulation, compared to conventional training, are able to achieve proficiency sooner with better patient outcomes. Design, setting, and participants: This international, multicentre, randomised controlled trial recruited 94 urology residents with experience of zero to ten procedures and no prior exposure to simulation in ureterorenoscopy, selected as an index procedure. Intervention: Participants were randomised to simulation or conventional operating room training, as is the current standard globally, and followed for 25 procedures or over 18 mo. Outcome measurements and statistical analysis: The number of procedures required to achieve proficiency, defined as achieving a score of ≥28 on the Objective Structured Assessment of Technical Skill (OSATS) scale over three consecutive operations, was measured. Surgical complications were evaluated as a key secondary outcome. This trial is registered at www.isrctn.com as ISCRTN 12260261. Results and limitations: A total of 1140 cases were performed by 65 participants, with proficiency achieved by 21 simulation and 18 conventional participants over a median of eight and nine procedures, respectively (hazard ratio [HR] 1.41, 95% confidence interval [CI] 0.72–2.75). More participants reached proficiency in the simulation arm in flexible ureterorenoscopy, requiring a lower number of procedures (HR 0.89, 95% CI 0.39–2.02). Significant differences were observed in overall comparison of OSATS scores between the groups (mean difference 1.42, 95% CI 0.91–1.92; p < 0.001), with fewer total complications (15 vs 37; p = 0.003) and ureteric injuries (3 vs 9; p < 0.001) in the simulation group. Conclusions: Although the number of procedures required to reach proficiency was similar, simulation-based training led to higher overall proficiency scores than for conventional training. Fewer procedures were required to achieve proficiency in the complex form of the index procedure, with fewer serious complications overall. Patient summary: This study investigated the effect of simulation training in junior surgeons and found that it may improve performance in real operating settings and reduce surgical complications for complex procedures.

We present a combined experimental and numerical investigation of the plasma properties in an asymmetric capacitively coupled radio frequency plasma source using argon discharge. Besides driving the system in the conventional way, which results in a high negative self-bias voltage V DC due to the asymmetric configuration, we also connect a ‘quarter-wavelength filter’ to the powered electrode, which lifts its DC potential to zero. At the powered side of the plasma, we employ electrodes with conducting and insulating surfaces, as well as electrodes combining both in different proportions (‘hybrid electrodes’). Measurements are carried out for the plasma potential, the electron density and temperature in the bulk plasma, as well as for the flux-energy distribution of the ions at the grounded surface of the system. The nature of the surface of the powered electrode as well as the presence of the quarter-wavelength filter are found to highly influence the plasma potential, V p ‾ . For the electrode with a conducting surface V p ‾ ∼ 20 V and ∼150 V are found in the absence and the presence of the filter, respectively. For the electrode with an insulating surface, the self-bias voltage builds up directly at the plasma interface, thus the filter has no effect and a plasma potential of ∼20 V is found. For the electrodes with different conducting/insulating proportions of their surface, V p ‾ ranges between the above values. Particle-in-Cell/Monte Carlo Collisions calculations for identical conditions with hybrid electrodes predict double-peaked ion energy distribution at the powered electrode with peaks corresponding to e V p ‾ and e ( V p ‾ − V DC ) along with a lowering of the plasma potential (whencompared to wholly conducting electrode), a trend that is observed experimentally. These studies are of great importance for the application of similar plasma sources with in-situ cleaning of mirrors in fusion devices and the results can be extended to a variety of plasma processing applications.

Am 16. August 2012 verstarb Prof. Dr. phil. Claus Vogel in Saarbrücken im Alter von 79 Jahren. Er war ordentliches Mitglied der Nordrhein-Westfälischen Akademie der Wissenschaften, gewählter Fellow der Royal Asiatic Society, London, Vorstandsvorsitzender der Helmuth von Glasenapp Stiftung, aber auch seit mehr als einem halben Jahrhundert Mitglied der DMG.

Conformational isomers are stereoisomers that can interconvert over low potential barriers by rotation around a single bond. However, such bond rotation is hampered by geometrical constraints when molecules are adsorbed on surfaces. Here we show that the adsorption of 4,4'-bis(4-carboxyphenyl)-6,6'-dimethyl-2,2'-bipyridine molecules on surfaces leads to the appearance of pro-chiral single-molecules on NiO(001) and to enantiopure supramolecular domains on Au(111) surfaces containing the $transoid$ molecule conformation. Upon additional Fe adatom deposition, molecules undergo a controlled interconversion from a $transoid$ to $cisoid$ conformation as a result of coordination of the Fe atoms to the 2,2'-bipyridine moieties. As confirmed by atomic force microscopy images and X-ray photoelectron spectroscopy measurements, the resulting molecular structures become irreversibly achiral.

This work aims at investigating the role of tungsten and boron surfaces on ammonia production with N2–H2 radiofrequency plasmas at 3 Pa. The experiments combine the analysis of the reaction products and surface chemical environment using mass spectrometry and x-ray photoelectron spectroscopy (XPS). We show that NH3 is formed upon discharges of N2 or H2 after having exposed a tungsten (W) foil to H2 or N2, respectively. A higher amount of ammonia is formed for the N2-then-H2 case, which we explain by the larger number of Eley–Rideal reaction channels for the formation of NH x (s) and the lower surface diffusion barrier for adsorbed hydrogen, calculated using the density functional theory (DFT). As a result, H(s) combines with N(s) or NH x (s) through Langmuir–Hinshelwood at a faster rate than N(s) combines with another N(s). The amount of NH3 formed with N2–H2 discharges after conditioning the tungsten foil with H2, N2 or O2 was also investigated. We observed that this pre-conditioning plays no major role on the amount of NH3 detected with the residual gas analyser, albeit a small decrease was observed after H2 contamination. With DFT, the adsorption energies of H on WO3 and W are found to be similar, while the adsorption of N on WO3 is significantly weaker. The similar NH3 concentrations obtained with a clean and oxidized tungsten surface thus suggest that the adsorption of N does not limit the formation rate of ammonia. The production of NH3 on boron was evaluated as well. The boron surface reduced the amount of detected ammonia almost by half. On the one side, a significant amount of H2 was removed from the surface during the Ar cleaning that followed, which suggests a strong retention of hydrogen. On the other side, the XPS data reveals that nitrogen forms strong bonds with boron and impurities on the surface, regardless on whether hydrogen is previously present on the surface or in the plasma volume. The presence of hydrogen in the plasma volume, simultaneously with nitrogen or after nitrogen exposure, is nevertheless necessary for the formation of NH(s) and NH2(s). No NH3(s) was however detected with XPS. The increased retention of both hydrogen and nitrogen on the boron surface may thus hinder the formation of NH3.

In ITER, several first mirrors (FMs) are expected to be DC-grounded with the water cooling lines being implemented as a quarter wavelength ($lambda$/4) RF-filter. DC-grounding of the FMs can significantly increase the plasma potential V p, which could trigger an increased wall sputtering and associated re-deposition on the FMs during plasma cleaning. To understand the scope of this impact, helium discharges were excited with DC-grounded FMs in an ITER-sized mock-up of a first mirror unit (FMU) using wall materials with different sputtering energy thresholds (E th). Additionally, a part of the FM was electrically isolated from the RF to study its impact on the erosion/re-deposition properties on the surface. The E th of the wall materials, as well as its native oxide layers, had a significant influence on the re-deposition observed on the FMs. With high E th where walls were unsputtered, both the DC-grounded and electrically isolated parts of the FM were free of deposits. However, with low E th where the walls were sputtered, there was a net wall re-deposition on the DC-grounded parts of the FM, while electrically isolated parts were still relatively clean. Further, to study the impact of floating wall components, Cu walls in the FMU were isolated from the ground. Here the walls developed a floating potential V f and the ion energy at the walls was lowered to e(V p - V f). The floating walls, in this case, were relatively unsputtered and the FMs experienced a net cleaning with total reflectivity of the mirror preserved at pristine mirror levels. This work shows that electrically isolating the FM as well as the wall surface minimizes wall re-deposition in presence of $lambda$/4 filter and therefore are promising techniques for effective FM cleaning in ITER.

This paper presents the measurement of the bidirectional reflectance distribution function of tungsten (W) samples and the resulting reflection models in the nuclear fusion device WEST (tokamak). For this, an experimental gonio-spectrophotometer was developed to fully characterize the material’s optical and thermal-radiative properties of metallic samples with different roughnesses. Ray-tracing photonic simulation was then carried out to predict the photon behavior in a fully metallic environment as a function of reflectance measurement. Low emissivity (0.1 at 4 μm) and highly specular reflectance (fitting with a Gaussian distribution around the specular direction with a small width lower than 10°) are found for W samples. These measurements have been used as input for the photonic simulation, and the resulting synthetic image reproduced the reflection features well on the upper divertor, detected in WEST infrared experimental images.

Templating insulating surfaces at the nanoscale is an interesting prospect for applications that involve the adsorption of molecules or nanoparticles where electronic decoupling of the adsorbed species from the substrate is needed. In this study, we present a method to structure alkali halide surfaces at the nanoscale using a combination of low temperature plasma exposure and annealing, and characterize the surfaces by atomic force microscopy. We find that nanostructurating can be controlled by the duration of the exposure, the atomic mass of the plasma gas and the subsequent step-by-step annealing process. In contrast to previous studies with electron or high energy (few keV) ion irradiation, our approach of employing moderate particle energy (10–15 eV Ar+ or He+ ions) results in fine nanostructuring at length scales of nanometers and even single atom vacancies.

Cleaning techniques for metallic first mirrors are needed in more than 20 optical diagnostic systems from ITER to avoid reflectivity losses. Plasma sputtering is considered as one of the most promising techniques to remove deposits coming from the main wall (mainly beryllium and tungsten). Previous plasma cleaning studies were conducted on mirrors contaminated with beryllium and tungsten where argon and/or helium were employed as process gas, demonstrating removal of contamination and recovery of optical properties. Still, both above-mentioned process gases have a non-negligible sputtering yield on mirrors. In this work, we explored the possibility to use a sputter gas having a small impact on mirrors while being efficient on Be deposits, e.g. deuterium. Two sputtering regimes were studied, on laboratory deposits as well as on mirrors exposed in JET-ILW, namely physical sputtering (220 eV ion energy) and chemically assisted physical sputtering (60 eV ion energy) using capacitively coupled plasma with radio frequency. The removal of Be and mixed Be/W contaminants, as well as the recovery of reflectivity, was achieved when deuterium was employed at 220 eV while cleaning at 60 eV was only fully efficient on laboratory beryllium deposits. On mirrors exposed in JET-ILW, the situation is more complex due to the presence of tungsten in the contaminant film, leading to the formation of a tungsten enriched surface that is not easily sputtered, especially at 60 eV.