Phase Stability Research Articles

Exploring microstructural evolution, nitrogen depth profile, and dry wear performance in 31CrMoV9 steel through combined severe shot peening and plasma nitriding

The present study investigates the influence of severe shot peening (SSP) on the plasma nitriding behavior and sliding wear performance of 31CrMoV9 steel. Initially, the steel was austenitized at 880 °C, followed by oil quenching, and tempering at 520 °C for one hour. These samples were shot peened using high-carbon steel shots, resulting in an enhancement in surface hardness up to 447 HV, gradually converging to the initial martensitic hardness after 140 µm depth. X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) scrutinized the initial and surface treated martensitic samples. Afterward, the plasma nitriding treatments were carried out at temperatures of 400 °C, 450 °C, and 500 °C for 8 hours in a 30% N2 + 70% H2 atmosphere and 300 Pa pressure. Microhardness testing, SEM, XRD, and glow-discharge optical emission spectroscopy (GDOES) evaluated both plasma nitrided (PN) and severe shot peened/plasma nitrided (SSP-PN) samples. Cross-sectional SEM observations revealed compound layer thicknesses of approximately 2.8 µm, 5.0 µm, and 6.3 µm for PN samples at 400 °C, 450 °C, and 500 °C, respectively. SSP-PN samples exhibited a substantial increase — roughly 71%, 44%, and 33% increase, respectively, compared to PN samples. GDOES analysis supported this trend and indicated enhanced nitrogen diffusion depth, particularly evident in SSP-PN samples at consistent temperatures. The XRD results showed the stability of Fe4N, Fe2–3N, and CrN phases at all three nitriding temperatures. Furthermore, the intensity of these phases increases with temperature and is augmented by the application of the SSP. Microhardness measurements indicated hardness escalation: from 775 HV to 980 HV at 400 °C, 932 HV to 1096 HV at 450 °C, and 1011 HV to 1205 HV at 500 °C due to SSP. Finally, the wear performance was investigated between the non-nitrided, SSP, PN, SSP-PN, samples. Initially, SSP led to decreased wear performance up to 500 m, followed by improved behavior up to 1500 m. At 400 °C, the SSP-PN sample exhibited a 12% lower wear rate than PN. At 450 °C and 1500 m, the SSP-PN sample displayed a 24% reduction, while at 500 °C, it showed a 27% reduction compared to PN. SEM observations indicated abrasion as the primary wear mechanism across all samples. The overall results indicated a significant similarity in the nitrogen depth profile, hardness depth, and wear performance between the SSP-PN sample at 450 °C and the PN sample at 500 °C. The fact suggested a potential reduction of approximately 50 °C in the typical plasma nitriding temperature for 31CrMoV9 steel as a result of the SSP process.

Crystallization management and defect passivation via additive engineering for efficient and stable carbon-based CsPbI2Br perovskite solar cells

Inorganic CsPbI2Br perovskite solar cells (PSCs) have attracted enormous interest due to their excellent thermal stability and immense potential for application in tandem solar cells. However, the rambunctious crystallization and poor film quality of inorganic CsPbI2Br perovskite are the main factors limiting their performance improvement. Herein, dibenzoylmethane (DBM), containing electron-rich and dual CO functional groups, as an efficient precursor additive, is first introduced to regulate the crystallization of CsPbI2Br perovskite while passivating its associated defects. After DBM modification, nucleation is accelerated and the crystallinity of CsPbI2Br film is improved, thus promoting the phase stability. Additionally, DBM can passivate uncoordinated Pb2+ defects, thereby significantly reducing non-radiative recombination, and can also decrease the energy level difference between CsPbI2Br/Carbon. As a result, when DBM additive is incorporated in the CsPbI2Br, the power conversion efficiency (PCE) of the device with the fluorine doped tin oxide glass (FTO)/SnO2/CsPbI2Br/Carbon structure is significantly improved to 13.46 %, an increase of nearly 13 % compared to the control device (11.72 %). The unpackaged devices exhibit excellent air and thermal stability, still remaining over 90 % of its initial PCE after aging for 500 h under ambient conditions, or continuous heating at 65 °C in glovebox for 500 h, respectively.

An Advanced Quality Assessment and Monitoring of ESA Sentinel-1 SAR Products via the CyCLOPS Infrastructure in the Southeastern Mediterranean Region

The Cyprus Continuously Operating Natural Hazards Monitoring and Prevention System, abbreviated CyCLOPS, is a national strategic research infrastructure devoted to systematically studying geohazards in Cyprus and the Eastern Mediterranean, Middle East, and North Africa (EMMENA) region. Amongst others, CyCLOPS comprises six permanent sites, each housing a Tier-1 GNSS reference station co-located with two calibration-grade corner reflectors (CRs). The latter are strategically positioned to account for both the ascending and descending tracks of SAR satellite missions, including the ESA’s Sentinel-1. As of June 2021, CyCLOPS has reached full operational capacity and plays a crucial role in monitoring the geodynamic regime within the southeastern Mediterranean area. Additionally, it actively tracks landslides occurring in the western part of Cyprus. Although CyCLOPS primarily concentrates on geohazard monitoring, its infrastructure is also configured to facilitate the radiometric calibration and geometric validation of Synthetic Aperture Radar (SAR) imagery. Consequently, this study evaluates the performance of Sentinel-1A SAR by exploiting the CyCLOPS network to determine key parameters including spatial resolution, sidelobe levels, Radar Cross-Section (RCS), Signal-to-Clutter Ratio (SCR), phase stability, and localization accuracy, through Point Target Analysis (PTA). The findings reveal the effectiveness of the CyCLOPS infrastructure to maintain high-quality radiometric parameters in SAR imagery, with consistent spatial resolution, controlled sidelobe levels, and reliable RCS and SCR values that closely adhere to theoretical expectations. With over two years of operational data, these findings enhance the understanding of Sentinel-1 SAR product quality and affirm CyCLOPS infrastructure’s reliability.

Growth and Redox Properties of Boron on Al(111): Competing Affinities in the Case of Honeycomb AlB2.

The complexity of the geometric and electronic structure of boron allotropes is associated with the multicentric bonding character and the consequent B polymorphism. When growth is limited to two-dimensions (2D), the structural and electronic confinement yields the borophenes family, where the interaction with the templating substrate actually determines the stability of inequivalent boron phases. We report here a detailed study of the growth of the honeycomb AlB2 phase on Al(111), followed by an investigation of its oxidation and reduction properties. By means of a combined experimental and theoretical approach, we show that the structure of the B/Al interface is affected by the complex interplay between B, Al, and common reactive agents like oxygen and hydrogen. While kinetic effects associated with diffusion and strain release influence the AlB2 growth in vacuo, Al, B, O, and H chemical affinities determine its redox behavior. Reduction with atomic hydrogen involves the B layer and yields an ordered honeycomb borophane H/AlB2 phase. Instead, oxidation takes place at the Al interface, giving origin to buried and 1D surface aluminum oxide phases.

Comprehensive analysis of the phase stability, optoelectronic, mechanical, thermodynamic, and vibrational properties for prospective optoelectronic applications of novel combinations of chalcogenides XScTe2 (X = Li, Rb) by employing density functional theory

Comprehensive analysis of the phase stability, optoelectronic, mechanical, thermodynamic, and vibrational properties for prospective optoelectronic applications of novel combinations of chalcogenides XScTe2 (X = Li, Rb) by employing density functional theory

Revisiting thermodynamics in (LiF, NaF, KF, CrF2)–CrF3 by first-principles calculations and CALPHAD modeling

The thermodynamic description of the (LiF, NaF, KF, CrF2)–CrF3 systems has been revisited, aiming for a better understanding of the effects of Cr on the FLiNaK molten salt. First-principles calculations based on density functional theory (DFT) were performed to determine the electronic and structural properties of each compound, including the formation enthalpy, volume, and bulk modulus. DFT-based phonon calculations were carried out to determine the thermodynamic properties of compounds, for example, enthalpy, entropy, and heat capacity as functions of temperature. Phonon-based thermodynamic properties show a good agreement with experimental data of binary compounds LiF, NaF, KF, CrF3, and CrF2, establishing a solid foundation to determine thermodynamic properties of ternary compounds as well as to verify results estimated by the Neumann-Kopp rule. Additionally, DFT-based ab initio molecular dynamics (AIMD) simulations were employed to predict the mixing enthalpies of liquid salts. Using DFT-based results and experimental data in the literature, the (LiF, NaF, KF, CrF2)–CrF3 system has been remodeled in terms of the CALculation of PHAse Diagrams (CALPHAD) approach using the modified quasichemical model with quadruplet approximation (MQMQA) for liquid. Calculated phase stability in the present work shows an excellent agreement with experiments, indicating the effectiveness of combining DFT-based total energy, phonon, and AIMD calculations, and CALPHAD modeling to provide the thermodynamic description in complex molten salt systems.

Influence of Severe Plastic Deformation on the Magnetic Properties of Sm–Co Permanent Magnets

High pressure torsion (HPT) is presented as a new fabrication route to produce bulk Sm–Co magnets with a strongly refined microstructure down to the nanometer regime. The initial powders, based on the compositions SmCo5, Sm2Co7 and Sm2Co17, are compacted and subsequently deformed by HPT. The microstructural evolution in dependence on the applied deformation parameters is characterized by electron microscopy and the effect of HPT on the phase stability is monitored by synchrotron X‐ray diffraction. An increasing amount of applied strain leads to a stronger reduction in grain size while strain localization counteracts a homogeneous microstructural refinement. The positive effect of elevated deformation temperatures is demonstrated for Sm2Co17, which promotes homogeneous grain refinement, but causes strain‐induced phase transformations at the same time, strongly affecting the magnetic behavior. Superconducting quantum interference device magnetometry is used to characterize the magnetic properties after HPT deformation, which indicates the formation of a magnetic texture depending on the respective phase.

Enhancement of Phase Stability and Thermoelectric Performance of Meta‐Stable AgSbTe2 by Thermal Cycling Process

AbstractThermoelectric materials are crucial components in thermoelectric devices employed for environmentally friendly solid‐state cooling and waste heat recovery, demanding not only high performance but also superior thermal or phase stability. The high‐performance thermoelectric material AgSbTe2 encounters challenges when utilized in thermoelectric modules due to the precipitation of Ag2Te, resulting in both thermally unstable characteristics and diminished performance. In this study, a thermal cycling process is employed to enhance the thermal stability and thermoelectric performance of AgSbTe2. Through thermal cycling, secondary phases of AgSbTe2 are made uniform, and the undesired Ag2Te is substituted with Sb2Te3 using an optimized thermal cycling process. As a result, the thermal stability of AgSbTe2 is enhanced due to its meta‐stable state, with <5% variance in thermoelectric figure of merit (ZT) measurements, and the ZT value is raised from 0.8 to 1.7 at 643 K through the optimized thermal cycling. The findings indicate that thermal cycling is an effective strategy for enhancing the thermal stability and thermoelectric performance of AgSbTe2, presenting a novel approach for achieving uniform secondary phases in materials with phase separation or phase change characteristics.

Spatial-to-spectral phase coupling mechanisms in bulk continuum generation

We study the coherence properties of continuum generation in YAG crystals seeded by 180 fs pulses at 1035 nm when the driving beam exhibits small fluctuations of the spatial phase. The relative stability of the continuum spectral phase is first assessed as a function of the driver wavefront aberrations. Furthermore, we evidence and quantify a coupling mechanism between these fluctuations and the spectral phase of the continuum. The coupling coefficients increase with the spectral broadening and are also unexpectedly large (up to tens of rad/rad at ≃ 750 nm). Experimental evidence supports that longitudinal shifts of the position of the filament within the crystal are responsible for such strong effects.

Optimization of the performance of CsPbI2Br perovskite solar cells in air by adding polyethylene-graft-maleic anhydride and its mechanism

In this study, by adding Polyethylene-graft-maleic anhydride (PGMA) to the inorganic CsPbI2Br perovskite film, the coordination bonds and hydrogen bonds between PGMA and CsPbI2Br cooperate to passivate defects, regulate energy level and stabilize the perovskite structure and eventually improve the device performance. We systematically study the effects of PGMA addition on the morphology, structure, light absorption, defect concentration and carrier lifetime, hydrophobicity, and optical stability and room temperature black phase stability of CsPbI2Br films, and the photoelectric performance and air stability of PSCs, as well as their mechanism. The experimental results show that the addition of 3 wt% of PGMA greatly improves the photoelectric conversion efficiency (PCE) of CsPbI2Br PSCs by 40.19 % because of the synergistic passivation effects and energy level tuning. The hydrogen bonds between –CH2 in PGMA and I−/Br− in CsPbI2Br, along with the coordination of carbonyl groups with Cs+/Pb2+, improve carrier transport and collection by inactivating flaw and managing the level, reducing the non-radiative recombination losses. In addition, the PSCs with 3 wt% of PGMA maintain 80 % of their initial efficiency even after 600 h in high humidity air environment due to the synergistic effect of coordination bonds and hydrogen bonds. Our study provides valuable insights into the use of PGMA to improve the performance of all-inorganic CsPbI2Br PSCs and the practicality of perovskite solar cells.

Phase Transition Thermodynamics of 1,3,5-Tris-(α-naphthyl)benzene: Theory and Experiment.

1,3,5-Tris-(α-naphthyl)benzene is an organic non-electrolyte with notable stability of an amorphous phase. Its glassy and supercooled liquid states were previously studied by spectroscopic and calorimetric methods. Despite the continuing interest in its amorphous state and, particularly, vapor-deposited glasses, the thermodynamic parameters of the vaporization of 1,3,5-tris-(α-naphthyl)benzene have not been obtained yet. Likewise, the reliable evaluation of the thermodynamic parameters of fusion below the melting point, required to establish the thermodynamic state of its glass, is still an unsolved problem. In this work, the heat capacities of crystalline and liquid phases, the temperature dependence of the saturated vapor pressures, fusion and vaporization enthalpies were determined using differential and fast scanning calorimetry and were verified using the estimates based on solution calorimetry. The structural features of 1,3,5-tris-(α-naphthyl)benzene are discussed based on the computations performed and the data on the molecular refractivity. The consistency between the values obtained by independent techniques was demonstrated.

Phase stability and physical behaviour of Fe3Pd, FePd and FePd3 binary intermetallic compounds

The FP-LAPW method is used to examine the physical properties of Fe–Pd binary intermetallic compounds. The calculated formation enthalpies indicate that FePd and FePd3 compounds are thermodynamically stable in L10 and L12 phases, respectively, and the ferromagnetic Fe3Pd can be formed in a tetragonal Z1 structure with a small negative formation enthalpy. The elastic coefficients and their related parameters show that all compounds are mechanically stable and ductile in nature. The FePd-L10 is the harder compound and Fe3Pd-Z1 exhibits the highest anisotropy. The band structure, the TDOS profile and the charge density distribution show that these compounds are ferromagnetic with a metallic character and covalent-metallic bonds. The PDOS shows that the Pd-4d and Fe-3d states are dominant, and the asymmetry of Fe-3d states is behind the system strong spin polarization. The calculated magnetic moments agree well with previous theoretical results. The thermodynamic parameters are determined using the quasi-harmonic Debye model.

The key role of methylenediammonium and tetrahydrotriazinium in the phase stability of FAPbI3

Formamidinium lead triiodide (FAPbI3) is the prime candidate for single-junction perovskite solar cells, despite the metastability of the phase. To improve its ambient-phase stability and produce world-record photoelectric conversion efficiencies, methylenediammonium (MDA) has been used as an additive in FAPbI3. However, the exact function and role of MDA are still uncertain. The MDA doping may exist in the perovskite lattice in either the original structure or the THTZ-H (tetrahydrotriazinium) structure. In this research, the effects of the MDA and THTZ-H doping FAPbI3 perovskite on its stability are explored by first-principles calculations. Both MDA and THTZ-H doping can improve the stability of FAPbI3 perovskite from a structural perspective due to lattice strain and stronger H–I bonds. However, the doping mechanisms differ significantly in terms of electronic properties. The MDA doping acts by the traditional passivation mechanism. It can eliminate the iodine interstitial defect states that trap charge carriers and inhibit iodine interstitial defect migration. The THTZ-H cation can directly contribute to the band edge construction in the FAPbI3 bulk. Electron delocalization in the π-conjugated ring structure lowered the frontier orbital separation of the THTZ-H organic molecule and enabled orbital overlap with the inorganic moiety. The in-depth understanding of the mechanism of improving stability in this study would facilitate the application of FAPbI3 perovskite optoelectronic devices.

Soft Lattice and Phase Stability of α‐FAPbI3

Soft Lattice and Phase Stability of α‐FAPbI₃

Gas‐Phase Formation of Sulfurous Acid (H2SO3) in the Atmosphere

Sulfurous acid (H2SO3) is known to be thermodynamically instable decomposing into SO2 and H2O. All attempts to detect this elusive acid in solution failed up to now. Reported H2SO3 formation from an experiment carried out in a mass spectrometer as well as results from theoretical calculations, however, indicated a possible kinetic stability in the gas phase. Here, it is shown experimentally that H2SO3 is formed in the OH radical‐initiated gas‐phase oxidation of methanesulfinic acid (CH3S(O)OH) at 295 ± 0.5 K and 1 bar of air with a molar yield of [[EQUATION]] %. Further main products are SO2, SO3 and methanesulfonic acid. CH3S(O)OH represents an important intermediate product of dimethyl sulfide oxidation in the atmosphere. Global modeling predicts an annual H2SO3 production of ∼8 million metric tons from the OH + CH3S(O)OH reaction. The investigated H2SO3 depletion in the presence of water vapor results in k(H2O + H2SO3) < 3 × 10‐18 cm3 molecule‐1 s‐1, which indicates a lifetime of at least one second for atmospheric humidity. This work provides experimental evidence that H2SO3, once formed in the gas phase, is kinetically stable enough to allow its characterization and subsequent reactions.

Gas-Phase Formation of Sulfurous Acid (H2SO3) in the Atmosphere.

Sulfurous acid (H2SO3) is known to be thermodynamically instable decomposing into SO2 and H2O. All attempts to detect this elusive acid in solution failed up to now. Reported H2SO3 formation from an experiment carried out in a mass spectrometer as well as results from theoretical calculations, however, indicated a possible kinetic stability in the gas phase. Here, it is shown experimentally that H2SO3 is formed in the OH radical-initiated gas-phase oxidation of methanesulfinic acid (CH3S(O)OH) at 295 ± 0.5 K and 1 bar of air with a molar yield of [[EQUATION]] %. Further main products are SO2, SO3 and methanesulfonic acid. CH3S(O)OH represents an important intermediate product of dimethyl sulfide oxidation in the atmosphere. Global modeling predicts an annual H2SO3 production of ∼8 million metric tons from the OH + CH3S(O)OH reaction. The investigated H2SO3 depletion in the presence of water vapor results in k(H2O + H2SO3) < 3 × 10-18 cm3 molecule-1 s-1, which indicates a lifetime of at least one second for atmospheric humidity. This work provides experimental evidence that H2SO3, once formed in the gas phase, is kinetically stable enough to allow its characterization and subsequent reactions.

Investigations on Growth, Characterization, NCI-RDG, AIM, Molecular Docking and In-Silico ADME Properties of 1,2-Benzene Dicarboxylic Acid Anhydride

Superior single crystal of 1,2-benzene dicarboxylic acid anhydride additionally called Phthalic anhydride (PAN) was developed via solution growth at low temperatures. Single crystal X-ray diffraction investigation revealed the crystal system and unit cell characteristics. The phase stability and crystalline nature were uncovered by powder X-ray diffraction analysis. FT-IR examination was done for the titular material so as to survey the various functional groups. With the use of the VEDA program's relevant resources, vibrational assignments have been made on the concept of Potential Energy Distribution (PED). Density Functional Theory (DFT) was employed to smooth out the molecular structure of PAN and was additionally utilized to consider FT-IR spectrum at molecular level. Non covalent interactions reduced density gradient (NCI-RDG) analysis has been used for the prediction of the weak interaction in the actual space in terms of the electron density along with its derivatives for PAN. Atoms in Molecules (AIM) analysis was carried for out for PAN. The docking research of the small molecule (PAN) with target protein confirmed that this is a great molecule which docks nicely with numerous targets associated with Hypoxia Inducible Factor 1-α. The absorption, distribution, metabolism, excretion (ADME) characteristics have been calculated with the assist of online server preADMET.

CALPHAD-Based Modeling and Experimental Validation of Silicon Effect on the Solidification Behavior of Novel SiNb Cast Irons

AbstractThe low oxidation resistance of SiMo ductile cast irons used as exhaust manifold material at high temperatures necessitates the development of new generation ductile cast iron compositions. New alloy designs can be made using CALPHAD methodology, and solidification sequence, segregation and critical phase transformation temperatures can be determined, especially for the solidified bulk materials. Thus, in commercial practicality, castable compositions with a raised A1 temperature can be obtained. In this study, novel SiNb cast irons with varying silicon contents were developed as candidate materials for exhaust manifolds. Solidification sequence, microsegregation, phase transformations, equilibrium phases of hypereutectic compositions containing 4 to 7 wt pct Si were calculated by CALPHAD-based modeling. The bulk materials of the studied compositions were cast as Y blocks and metallurgical analyzes were carried out. Studies revealed that; (i) in the ferritic matrix of the cast irons, graphite, Nb-rich carbides and some pearlite existed, (ii) pearlite formation was due to the negative segregation of silicon and positive segregation of manganese during solidification, (iii) as silicon content increased the amount of silicon dissolved in ferrite phase increased in the solidified structure and as a result pearlite formation decreased at the cell boundaries, and amount of vermicular graphite increased, (iv) depending on the silicon content the critical A1 temperature varied between 860 °C to 1013 °C and these values were higher than that of SiMo cast iron. All these findings revealed that SiNb cast irons had phase stability at higher temperatures compared to SiMo cast iron.

Enhancement of Perovskite Photodetector Using MAPbI3 with Formamidinium Bromide

In this study, a perovskite-based mixed cation/anion ultraviolet photodetector with an added halide material is fabricated using perovskite combined with an ABX_3 structure. Mixed cation/anion perovskite thin films of MAPbI3/FABr are manufactured through a relatively simple solution process and employed as light-absorption layers. In the produced thin film, SnO2–sodium dodecylbenzenesulfonate acts as an electron transport layer and spiro-OMeTAD acts as a hole injection layer. Compared to a single cation/anion perovskite, the fabricated device exhibits phase stability and optoelectronic properties, and demonstrates a responsivity of 72.2 mA/W and a detectability of 4.67 × 1013 Jones. In addition, the films show an external quantum efficiency of 56%. This suggests that mixed cation/anion films can replace single cation/anion perovskite films. Thus, photodetectors based on lead halides that can be applied in various fields have recently been manufactured.

Stress-induced phase stability and optoelectronic property changes in cesium lead halide perovskites

Over the past decade, the certified power conversion efficiency of perovskite solar cells (PSCs) has increased to 26.1%. However, phase instability originating from lattice strains, has limited their commercialization. Strains will inevitably be generated during the PSC fabrication and service process due to the “soft lattice” nature of halide perovskites. In particular, flexible PSCs are subjected to not only mechanical tensile and compressive loads, but also suffer from thermal stresses. In this study, strain-induced changes in the phase stability and the corresponding optoelectronic properties of CsPbI3−xBrx (CsPbI3, CsPbBr3, and CsPbI2Br) systems under tensile and compressive stresses were investigated using first-principles calculations. The results showed that compressive stresses reduce the bandgap value and increase the light absorption coefficient; thus, the optoelectronic performance is improved, whereas the light absorption coefficient decreases regardless of how the bandgap changes under tensile stresses. Moreover, under the same stress, the tensile strain value was twice that of the compressive strain, and the critical value of the transition from the cubic to tetragonal phase was lower, indicating that phase stability was worse under tensile stresses. Therefore, during the fabrication of PSCs, the tensile stress state should be adjusted to the compressive stress state, which is favorable for enhancing PSCs photovoltaic performance and phase stability. The results not only provide direct evidence of tensile and compressive strains influencing the phase stability and optoelectronic property changes in halide perovskites, but also highlight lattice-strain tailoring for the composition design, process optimization, and interface engineering of efficient and stable PSCs.