A large body of work has been reported in the last 5 years on the development of lead‐free piezoceramics in the quest to replace lead–zirconate–titanate (PZT) as the main material for ...electromechanical devices such as actuators, sensors, and transducers. In specific but narrow application ranges the new materials appear adequate, but are not yet suited to replace PZT on a broader basis. In this paper, general guidelines for the development of lead‐free piezoelectric ceramics are presented. Suitable chemical elements are selected first on the basis of cost and toxicity as well as ionic polarizability. Different crystal structures with these elements are then considered based on simple concepts, and a variety of phase diagrams are described with attractive morphotropic phase boundaries, yielding good piezoelectric properties. Finally, lessons from density functional theory are reviewed and used to adjust our understanding based on the simpler concepts. Equipped with these guidelines ranging from atom to phase diagram, the current development stage in lead‐free piezoceramics is then critically assessed.
Influence of mean stress on fatigue life of the austenitic stainless steel 316 L in air and light water environments (boiling water reactor/hydrogen water chemistry) at 288 °C was determined with a ...series of tests carried out in load-control mode. Fatigue life was found to increase with application of compressive and tensile mean stress in air and light water reactor environments. Secondary hardening was regarded as the main reason for this behavior. A modified Smith-Watson-Topper (SWT) model was considered to account for mean stress and was shown to predict fatigue life accurately in air and water environments. The reduction of fatigue life in water environment, determined with the SWT curves, was about 2.5. Observations of the end-of-life dislocation arrangements by transmission electron microscopy showed that the dislocation microstructure depends essentially on plastic strain amplitude, which in turn is strongly correlated to stress amplitude and mean stress. The microstructures were found consistent with those usually observed after strain-controlled experiments. At rather low plastic strain amplitudes, corduroy structure consisting of small dislocation loops was observed. Acting as significant obstacle to dislocation motion, corduroy structure affects overall dislocation mobility therefore contributing to notable secondary cyclic hardening.
The polarization lidar photometer networking (POLIPHON) method introduced to separate coarse-mode and fine-mode particle properties of Eyjafjallajökull volcanic aerosols in 2010 is extended to cover ...Saharan dust events as well. Furthermore, new volcanic dust observations performed after the Grimsvötn volcanic eruptions in 2011 are presented. The retrieval of particle mass concentrations requires mass-specific extinction coefficients. Therefore, a review of recently published mass-specific extinction coefficients for Saharan dust and volcanic dust is given. Case studies of four different scenarios corroborate the applicability of the profiling technique: (a) Saharan dust outbreak to central Europe, (b) Saharan dust plume mixed with biomass-burning smoke over Cape Verde, and volcanic aerosol layers originating from (c) the Eyjafjallajökull eruptions in 2010 and (d) the Grimsvötn eruptions in 2011. Strong differences in the vertical aerosol layering, aerosol mixing, and optical properties are observed for the different volcanic events.
The task of learning a probability distribution from samples is ubiquitous across the natural sciences. The output distributions of local quantum circuits are of central importance in both quantum ...advantage proposals and a variety of quantum machine learning algorithms. In this work, we extensively characterize the learnability of output distributions of local quantum circuits. Firstly, we contrast learnability with simulatability by showing that Clifford circuit output distributions are efficiently learnable, while the injection of a single T gate renders the density modeling task hard for any depth d=n^{Ω(1)}. We further show that the task of generative modeling universal quantum circuits at any depth d=n^{Ω(1)} is hard for any learning algorithm, classical or quantum, and that for statistical query algorithms, even depth d=ωlog(n) Clifford circuits are hard to learn. Our results show that one cannot use the output distributions of local quantum circuits to provide a separation between the power of quantum and classical generative modeling algorithms, and therefore provide evidence against quantum advantages for practically relevant probabilistic modeling tasks.
Cloud properties from both ground-based as well as from geostationary passive satellite observations have been used previously for diagnosing aerosol–cloud interactions. In this investigation, a ...2-year data set together with four selected case studies are analyzed with the aim of evaluating the consistency and limitations of current ground-based and satellite-retrieved cloud property data sets. The typically applied adiabatic cloud profile is modified using a sub-adiabatic factor to account for entrainment within the cloud. Based on the adiabatic factor obtained from the combination of ground-based cloud radar, ceilometer and microwave radiometer, we demonstrate that neither the assumption of a completely adiabatic cloud nor the assumption of a constant sub-adiabatic factor is fulfilled (mean adiabatic factor 0.63 ± 0.22). As cloud adiabaticity is required to estimate the cloud droplet number concentration but is not available from passive satellite observations, an independent method to estimate the adiabatic factor, and thus the influence of mixing, would be highly desirable for global-scale analyses. Considering the radiative effect of a cloud described by the sub-adiabatic model, we focus on cloud optical depth and its sensitivities. Ground-based estimates are here compared vs. cloud optical depth retrieved from the Meteosat SEVIRI satellite instrument resulting in a bias of −4 and a root mean square difference of 16. While a synergistic approach based on the combination of ceilometer, cloud radar and microwave radiometer enables an estimate of the cloud droplet concentration, it is highly sensitive to radar calibration and to assumptions about the moments of the droplet size distribution. Similarly, satellite-based estimates of cloud droplet concentration are uncertain. We conclude that neither the ground-based nor satellite-based cloud retrievals applied here allow a robust estimate of cloud droplet concentration, which complicates its use for the study of aerosol–cloud interactions.
During the CONCERT 2011 field experiment with the DLR research aircraft Falcon, an enhanced aerosol layer with particle linear depolarization ratios of 6–8% at 532 nm was observed at altitudes above ...10 km over northeast Germany on 16 September 2011. Dispersion simulations with HYSPILT suggest that the elevated aerosol layer originated from the Pagami Creek forest fire in Minnesota, USA, which caused pyro-convective uplift of particles and gases. The 3–4 day-old smoke plume had high total refractory black carbon (rBC) mass concentrations of 0.03–0.35 μg m−3 at standard temperature and pressure (STP) with rBC mass equivalent diameter predominantly smaller than 130 nm. Assuming a core-shell particle structure, the BC cores exhibit very thick (median: 105–136 nm) BC-free coatings. A large fraction of the BC-containing particles disintegrated into a BC-free fragment and a BC fragment while passing through the laser beam of the Single Particle Soot Photometer (SP2). In this study, the disintegration is a result of very thick coatings around the BC cores. This is in contrast to a previous study in a forest-fire plume, where it was hypothesized to be a result of BC cores being attached to a BC-free particle. For the high-altitude forest-fire aerosol layer observed in this study, increased mass specific light-absorption cross sections of BC can be expected due to the very thick coatings around the BC cores, while this would not be the case for the attached-type morphology. We estimate the BC mass import from the Pagami Creek forest fire into the upper troposphere/lower stratosphere (UTLS) region (best estimate: 25 Mg rBC). A comparison to black carbon emission rates from aviation underlines the importance of pyro-convection on the BC load in the UTLS region. Our study provides detailed information on the microphysics and the mixing state of BC in the forest-fire aerosol layer in the upper troposphere that can be used to better understand and investigate the radiative impact of such upper tropospheric aerosol layers.
The synthesis of linear symmetric ethynyl‐ and acetylide‐amidinates of the coinage metals is presented. Starting with the desilylation of the complexes {Me3SiC≡CC(NDipp)2}2M2 ...(Dipp=2,6‐diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n‐butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form {(PPh3)AuC≡CC(NDipp)2}2M2 (M=Cu, Au). The corresponding Ag complex {(PPh3)AuC≡CC(NDipp)2}2Ag2 was obtained by a different route via metal rearrangement. All compounds show bright blue or blue‐green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20–295 K. Emission quantum yields of up to 41 % at room temperature were determined. Furthermore, similar emissions with quantum yields of 15 % were observed for the two most brightly luminescent complexes in thf solution.
Two plus two is four: The synthesis of linear symmetric ethynyl‐ and acetylide‐amidinates of the coinage metals is presented. Their photophysical properties were thoroughly investigated in a temperature range of 20–295 K. Short lifetimes and quantum yields of up to 41 % were determined. Furthermore, the complexes show pronounced PL in thf solution as well.
Structural integrity of reactor pressure vessels (RPV) is critical for safety and lifetime. Possible degradation of fracture resistance of RPV steel due to exposure to coolant and hydrogen is a ...concern. In this study tensile and elastic-plastic fracture mechanics (EPFM) tests in air (hydrogen pre-charged) and EFPM tests in hydrogenated/oxygenated high-temperature water (HTW) was done, using a low-alloy RPV steel. 2–5 wppm hydrogen caused embrittlement in air tensile tests at room temperature (25 °C) and at 288 °C, effects being more significant at 25 °C and in simulated weld coarse grain heat affected zone material. Embrittlement at 288 °C is strain rate dependent and is due to localized plastic deformation. Hydrogen pre-charging/HTW exposure did not deteriorate the fracture resistance at 288 °C in base metal, for investigated loading rate range. Clear change in fracture morphology and deformation structures was observed, similar to that after air tests with hydrogen.
•Hydrogen content, microstructure of LAS, and strain rate affects tensile properties at 288 °C.•Strength affects hydrogen embrittlement susceptibility to a greater extent than grain size.•Hydrogen in LAS leads to strain localization and restricts cross-slip at 288 °C.•Possible hydrogen pickup due to exposure to 288 °C water alters fracture surface appearance without affecting fracture toughness in bainitic base material.•Simulated weld heat affected zone microstructure shows unstable crack propagation in 288 °C water.
We previously showed that elevated TYMS exhibits oncogenic properties and promotes tumorigenesis after a long latency, suggesting cooperation with sequential somatic mutations. Here we report the ...cooperation of ectopic expression of human TYMS with loss of Ink4a/Arf, one of the most commonly mutated somatic events in human cancer. Using an hTS/Ink4a/Arf
genetically engineered mouse model we showed that deregulated TYMS expression in Ink4a/Arf null background accelerates tumorigenesis and metastasis. In addition, tumors from TYMS-expressing mice were associated with a phenotype of genomic instability including enhanced double strand DNA damage, aneuploidy and loss of G1/S checkpoint. Downregulation of TYMS in vitro decreased cell proliferation and sensitized tumor cells to antimetabolite chemotherapy. In addition, depletion of TYMS in vivo by TYMS shRNA reduced tumor incidence, delayed tumor progression and prolonged survival in hTS/Ink4a/Arf
mice. Our data shows that activation of TYMS in Ink4a/Arf null background enhances uncontrolled cell proliferation and tumor growth, supporting the development of new agents and strategies targeting TYMS to delay tumorigenesis and prolong survival.
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