Development of Thermodynamic Criteria for Determining the Composition of Duplex Stainless Steels with High Corrosion Resistance.

One of the most popular methods for ranking duplex stainless steels (DSSs) and predicting their corrosion properties is the calculation of the pitting resistance equivalent number (PREN). However, since DSSs are two-phase materials with a significant fraction of secondary phases and precipitates, the application of the PREN can be highly limited. This article attempted to use a new approach to describe the corrosion resistance of these steels. The corrosion resistance of two DSSs of the same class was investigated. Under identical solution heat treatments in the temperature range of 1050-1200 °C, the crevice corrosion resistance of one steel increased, while that of the other decreased. It was demonstrated that the amounts of austenite and ferrite changed similarly in these steels, and the different corrosion resistances were associated with the behaviors of secondary phases: niobium carbonitride and chromium nitride. SEM-EDS analysis was conducted to analyze the redistribution of elements between phases in both cases, showing good agreement with the thermodynamic modeling results. The PREN was calculated for each phase depending on the treatment temperature, and a method for calculating the effective PREN (PRENeff), accounting for phase balance and secondary phases, was proposed. It was shown that this indicator described corrosion properties better than the classical PREN calculated for the average steel composition. This study demonstrated how the calculation of critical temperatures (the temperature of equal amounts of ferrite and austenite, the temperature of the beginning of chromium nitride formation, and the temperature of the beginning of σ-phase formation) could describe the corrosion resistance of DSSs. Maximum possible deviations from these temperatures were defined, allowing the attainment of the required corrosion properties for the steels. Based on the conducted research, an approach for selecting new compositions of DSSs was proposed.

Possibilities of Controlling the Quantum States of Hole Qubits in an Ultrathin Germanium Layer Using a Magnetic Substrate: Results from ab Initio Calculations.

Using density functional theory in the noncollinear approximation, the behavior of quantum states of hole qubits in a Ge/Co:ZnO system was studied in this work. A detailed analysis of the electronic structure and the distribution of total charge density and hole states was carried out. It was shown that in the presence of holes, the energetically more favorable quantum state is the state |0˃, in contrast to the state |1˃ when there is no hole in the system. The favorability of hole states was found to be dependent on the polarity of the applied electric field.

Control of the Composition and Morphology of Non-Metallic Inclusions in Superduplex Stainless Steel.

Duplex stainless steel is a unique material for cast products, the use of which is possible in various fields. With the same chemical composition, melting, casting and heat treatment technology, pitting and crevice corrosion were observed at the interphase boundaries of non-metallic inclusions and the steel matrix. To increase the cleanliness of steel, it is necessary to carefully select the technology for deoxidizing with titanium or aluminum, as the most common deoxidizers, and the technology for modifying with rare earth metals. In this work, a comprehensive analysis of the thermodynamic data in the literature on the behavior of oxides and sulfides in this highly alloyed system under consideration was performed. Based on this analysis, a thermodynamic model was developed to describe their behavior in liquid and solidified duplex stainless steels. The critical concentrations at which the existence of certain phases is possible during the deoxidation of DSS with titanium, aluminum and modification by rare earth metals, including the simultaneous contribution of lanthanum and cerium, was determined. Experimental ingots were produced, the cleanliness of experimental steels was assessed, and the key metric parameters of non-metallic inclusions were described. In steels deoxidized using titanium, clusters of inclusions with a diameter of 84 microns with a volume fraction of 0.066% were formed, the volume fraction of which was decreased to 0.01% with the subsequent addition of aluminum. The clusters completely disappeared when REMs were added. The reason for this behavior of inclusions was interpreted using thermodynamic modeling and explained by the difference in temperature at which specific types of NMIs begin to form. A comparison of experimental and calculated results showed that the proposed model adequately describes the process of formation of non-metallic inclusions in the steel under consideration and can be used for the development of industrial technology.

Z-flipon variants reveal the many roles of Z-DNA and Z-RNA in health and disease.

Identifying roles for Z-DNA remains challenging given their dynamic nature. Here, we perform genome-wide interrogation with the DNABERT transformer algorithm trained on experimentally identified Z-DNA forming sequences (Z-flipons). The algorithm yields large performance enhancements (F1 = 0.83) over existing approaches and implements computational mutagenesis to assess the effects of base substitution on Z-DNA formation. We show Z-flipons are enriched in promoters and telomeres, overlapping quantitative trait loci for RNA expression, RNA editing, splicing, and disease-associated variants. We cross-validate across a number of orthogonal databases and define BZ junction motifs. Surprisingly, many effects we delineate are likely mediated through Z-RNA formation. A shared Z-RNA motif is identified in SCARF2, SMAD1, and CACNA1 transcripts, whereas other motifs are present in noncoding RNAs. We provide evidence for a Z-RNA fold that promotes adaptive immunity through alternative splicing of KRAB domain zinc finger proteins. An analysis of OMIM and presumptive gnomAD loss-of-function datasets reveals an overlap of Z-flipons with disease-causing variants in 8.6% and 2.9% of Mendelian disease genes, respectively, greatly extending the range of phenotypes mapped to Z-flipons.

Thermal Properties of Porous Silicon Nanomaterials.

The thermal properties, including the heat capacity, thermal conductivity, effusivity, diffusivity, and phonon density of states of silicon-based nanomaterials are analyzed using a molecular dynamics calculation. These quantities are calculated in more detail for bulk silicon, porous silicon, and a silicon aerocrystal (aerogel), including the passivation of the porous internal surfaces with hydrogen, hydroxide, and oxygen ions. It is found that the heat capacity of these materials increases monotonically by up to 30% with an increase in the area of the porous inner surface and upon its passivation with these ions. This phenomenon is explained by a shift of the phonon density of states of the materials under study to the low-frequency region. In addition, it is shown that the thermal conductivity of the investigated materials depends on the degree of their porosity and can be changed significantly upon the passivation of their inner surface with different ions. It is demonstrated that, in the various simulated types of porous silicon, the thermal conductivity changes by 1-2 orders of magnitude compared with the value for bulk silicon. At the same time, it is found that the nature of the passivation of the internal nanosilicon surfaces affects the thermal conductivity. For example, the passivation of the surfaces with hydrogen does not significantly change this parameter, whereas a passivation with oxygen ions reduces it by a factor of two on average, and passivation with hydroxyl ions increases the thermal conductivity by a factor of 2-3. Similar trends are observed for the thermal effusivities and diffusivities of all the types of nanoporous silicon under passivation, but, in that case, the changes are weaker (by a factor of 1.5-2). The ways of tuning the thermal properties of the new nanostructured materials are outlined, which is important for their application.

Development of a Methodology for the Quality Management of Duplex Stainless Steels.

The use of traditional materials leads to failures and breakdowns of expensive equipment, so advanced materials are needed that can provide reliable and durable solutions. The ability to control the quality of duplex stainless steels (DSSs) can greatly help with the development of new compositions or choosing existing DSSs. In this case, it is necessary to consider the final consumer properties-corrosion resistance and mechanical properties, which depend on the phase composition, contamination with non-metallic inclusions (NMIs), and the presence of undesirable secondary phases. In this research, specimens of cast DSSs of different grades, produced at laboratory and industrial scales, were studied. A technique for quantifying the microstructure of DSSs was developed. A thermodynamic database was chosen that adequately describes the processes of phase formation in DSSs. The effects of heat treatment on the microstructure and corrosion properties of cast DSSs were studied. The effects of the structural state on the changes in consumer properties of the final product are shown. It is shown that using various deoxidation technologies, it is possible to obtain both NMIs that are dangerous in terms of corrosive activity and ones that are relatively safe.

Charge-transfer plasmons of complex nanoparticle arrays connected by conductive molecular bridges.

Charge-transfer plasmons (CTP) in complexes of metal nanoparticles bridged by conductive molecular linkers are theoretically analysed using a statistic approach. The applied model takes into account the kinetic energy of carriers inside the linkers including its dissipation and the Coulomb energy of the charged nanoparticles. The plasmons are statistically investigated for systems containing a large number of complexes of bridged nanoparticles of realistic sizes generated using a simplified molecular dynamics algorithm, where the geometries of the complexes are dependent on the rate of connection of the linkers with the nanoparticles. As illustrated, the distribution of CTP frequencies in the generated nanoparticle complexes is very inhomogeneous. It has a narrow peak, corresponding to CTP plasmons in dimers, and two broad peaks, corresponding mainly to low and high-frequency oscillations in chains of connected nanoparticles. It is found that in general the plasmon frequencies depend inversely on the value of the complex dipole moment of the plasmon oscillation, where the assumption follows that low-frequency plasmons will be more efficiently excited in an external electromagnetic field. To calculate the CTP energy absorption in this field two model modifications are proposed: a system-external electromagnetic field interaction model and a simplified broadening plasmon peak model where the plasmons are calculated at first without damping and where the delta-shaped oscillation peaks are broadened then due to the damping. It is demonstrated that both modifications lead to a wide and almost monotonic absorption in the IR region for all generated systems containing a large number of bridged nanoparticles due to the presence of a large number of CTPs in this region.

ADAR1 masks the cancer immunotherapeutic promise of ZBP1-driven necroptosis.

Only a small proportion of patients with cancer show lasting responses to immune checkpoint blockade (ICB)-based monotherapies. The RNA-editing enzyme ADAR1 is an emerging determinant of resistance to ICB therapy and prevents ICB responsiveness by repressing immunogenic double-stranded RNAs (dsRNAs), such as those arising from the dysregulated expression of endogenous retroviral elements (EREs)1-4. These dsRNAs trigger an interferon-dependent antitumour response by activating A-form dsRNA (A-RNA)-sensing proteins such as MDA-5 and PKR5. Here we show that ADAR1 also prevents the accrual of endogenous Z-form dsRNA elements (Z-RNAs), which were enriched in the 3' untranslated regions of interferon-stimulated mRNAs. Depletion or mutation of ADAR1 resulted in Z-RNA accumulation and activation of the Z-RNA sensor ZBP1, which culminated in RIPK3-mediated necroptosis. As no clinically viable ADAR1 inhibitors currently exist, we searched for a compound that can override the requirement for ADAR1 inhibition and directly activate ZBP1. We identified a small molecule, the curaxin CBL0137, which potently activates ZBP1 by triggering Z-DNA formation in cells. CBL0137 induced ZBP1-dependent necroptosis in cancer-associated fibroblasts and reversed ICB unresponsiveness in mouse models of melanoma. Collectively, these results demonstrate that ADAR1 represses endogenous Z-RNAs and identifies ZBP1-mediated necroptosis as a new determinant of tumour immunogenicity masked by ADAR1. Therapeutic activation of ZBP1-induced necroptosis provides a readily translatable avenue for rekindling the immune responsiveness of ICB-resistant human cancers.

Mono a Mano: ZBP1's Love-Hate Relationship with the Kissing Virus.

Z-DNA binding protein (ZBP1) very much represents the nuclear option. By initiating inflammatory cell death (ICD), ZBP1 activates host defenses to destroy infectious threats. ZBP1 is also able to induce noninflammatory regulated cell death via apoptosis (RCD). ZBP1 senses the presence of left-handed Z-DNA and Z-RNA (ZNA), including that formed by expression of endogenous retroelements. Viruses such as the Epstein-Barr "kissing virus" inhibit ICD, RCD and other cell death signaling pathways to produce persistent infection. EBV undergoes lytic replication in plasma cells, which maintain detectable levels of basal ZBP1 expression, leading us to suggest a new role for ZBP1 in maintaining EBV latency, one of benefit for both host and virus. We provide an overview of the pathways that are involved in establishing latent infection, including those regulated by MYC and NF-κB. We describe and provide a synthesis of the evidence supporting a role for ZNA in these pathways, highlighting the positive and negative selection of ZNA forming sequences in the EBV genome that underscores the coadaptation of host and virus. Instead of a fight to the death, a state of détente now exists where persistent infection by the virus is tolerated by the host, while disease outcomes such as death, autoimmunity and cancer are minimized. Based on these new insights, we propose actionable therapeutic approaches to unhost EBV.

CuFeAl Nanocomposite Catalysts for Coal Combustion in Fluidized Bed.

A method of oil-drop granulation was suggested for the preparation of spherical CuFeAl nanocomposite catalysts. The catalysts were characterized by a set of physicochemical methods (X-ray diffraction, temperature-programmed reduction by H2, low-temperature nitrogen adsorption, crushing strength) and tested in the oxidation of CO and burning of brown coal in a fluidized bed. It was found that the catalysts have high mechanical strength (16.2 MPa), and their catalytic properties in the oxidation of CO are comparable to the characteristics of industrial Cr-containing catalysts. It was shown that the addition of pseudoboehmite at the stage of drop formation contributes to the production of uniform spherical high-strength granules and facilitates the stabilization of the phase state of the active component. The use of CuFeAl nanocomposite catalysts for the burning of brown coal provides a low emission of CO (600 ppm) and NOx (220 ppm) and a high degree of coal burnout (95%), which are close to those of the industrial Cr-containing catalysts (emission of CO is 700 ppm, NOx-230 ppm, and degree of coal burnout is 95%).

Effect of Oxygen Nonstoichiometry on Electrical Conductivity and Thermopower of Gd0.2Sr0.8FeO3-δ Ferrite Samples.

The behavior of the resistivity and thermopower of the Gd0.2Sr0.8FeO3-δ ferrite samples with a perovskite structure and the sample stability in an inert gas atmosphere in the temperature range of 300⁻800 K have been examined. It has been established that, in the investigated temperature range, the thermoelectric properties in the heating‒cooling mode are stabilized at δ ≥ 0.21. It is shown that the temperature dependencies of the resistivity obtained at different δ values obey the activation law up to the temperatures corresponding to the intense oxygen removal from a sample. The semiconductor‒semiconductor electronic transitions accompanied by a decrease in the activation energy have been observed with increasing temperature. It is demonstrated that the maximum thermoelectric power factor of 0.1 µW/(cm·K²) corresponds to a temperature of T = 800 K.

Crystal Structure Representation for Neural Networks using Topological Approach.

In the present work we describe a new approach, which uses topology of crystals for physicochemical properties prediction using artificial neural networks (ANN). The topologies of 268 crystal structures were determined using ToposPro software. Quotient graphs were used to identify topological centers and their neighbors. The topological approach was illustrated by training ANN to predict molar heat capacity, standard molar entropy and lattice energy of 268 crystals with different compositions and structures (metals, inorganic salts, oxides, etc.). ANN was trained using Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm. Mean absolute percentage error of predicted properties was ≤8 %.