Phase Diffusion Research Articles

Typology of Business Incubators in Spain According to the Stages of Startups Incubation

The aim of this work was to classify the business incubators in Spain according to the four phases of the startup’s incubation process. Considering that the graduation rate implies greater survival and business success of the incubated companies, they have been identified at each stage of the incubation (spread of entrepreneurship, pre-incubation, advanced incubation, and graduation). The activities that present higher impacts on the success of the incubated companies and the activities carried out by the business incubator that have a greater relevance on the graduation of the companies have concretely been considered. Principal component (PC) cluster analysis has been applied. All the incubation variables were used simultaneously, reducing their number and grouping them into factors. Finally, the cases were grouped according to these latent variables. Principal component analysis reduced dimensionality to eight factors with a 74% explained variance. Factor 1 was positively related to pre-incubation variables; factor 2 was linked to training and collaboration variables within the entrepreneurship diffusion phase. Factor 3, named activity monitoring and control, was related to phase 3, or basic incubation variables. Cluster analysis facilitates the grouping of business incubators into three clusters: Group 1 (16% of the total), incubators with strong deficits in incubation phases 1, 2, and 3. They are small-sized business incubators, often located in rural areas or cities, with a low graduation rate. Group 2 (30%), business incubators with a very high graduation rate and strongly positive values in factors 1 and 2. Factor 3, although positive, is susceptible to improvement. They are the largest group of business incubators and usually located in industrial and technological parks. Group 3 (54%) is the majority, with values close to clusters 2 and 3.

Influence of Electrolyte Saturation on the Performance of Li-O2 Batteries.

Electrolyte saturation can strongly affect the Li-O2 battery performance. However, it is unclear to what extent saturation reduction will impact the battery capacity. In this study, we investigated the influence of electrolyte saturation and distribution within a porous positive electrode on the deep discharge-charge capacities and cycling stability. The study used both models and experiments to investigate the change of electrolyte distribution, double-layer capacitance, ohmic resistance, and O2 concentration in the positive electrode at different electrolyte saturations. Results revealed that electrodes with 60% electrolyte saturation achieved almost the same maximum discharge (6.38 vs 6.76 mAh/cm2) and charge (5.52 vs 5.65 mAh/cm2) capacities with fully saturated electrodes. The partially wet positive electrode (40% saturation) obtained more cycles than the electrode with 100% saturation before the discharge capacity dropped below the cutoff point. However, the electrode with 40% saturation had a low average charging efficiency of 88.76%, whereas the fully saturated electrode obtained 98.96% charging efficiency. Moreover, the fully wet positive electrode had the lowest overpotential during cycling (1.26-1.39 V). The measured electrochemically active surface areas showed that even 40% saturation could sufficiently wet the positive electrode surface and obtain a double-layer capacitance (18.12 mF) similar to that with 100% saturation (20.4 mF). Furthermore, a considerable increase in O2 concentration at wetted surface areas was observed for the electrolyte saturation of less than 60% due to the significantly higher O2 diffusivity in the gas phase.

Phase and thermal diffusivity variation of saline water diagnosed by visual and temperature method during freezing process

Phase and thermal diffusivity variation of saline water diagnosed by visual and temperature method during freezing process

Microscopic mechanism of water-assisted diffusional phase transitions in inorganic metal halide perovskites.

The stability of perovskite materials is profoundly influenced by the presence of moisture in the surrounding environment. While it is well-established that water triggers and accelerates the black-yellow phase transition, leading to the degradation of the photovoltaic properties of perovskites, the underlying microscopic mechanism remains elusive. In this study, we employ classical molecular dynamics simulations to examine the role of water molecules in the yellow-black phase transition in a typical inorganic metal halide perovskite, CsPbI3. We have demonstrated, through interfacial energy calculations and classical nucleation theory, that the phase transition necessitates a crystal-amorphous-crystal two-step pathway rather than the conventional crystal-crystal mechanism. Simulations for CsPbI3 nanowires show that water molecules in the air can enter the amorphous interface between the black and yellow regions. The phase transition rate markedly increases with the influx of interfacial water molecules, which enhance ion diffusivity by reducing the diffusion barrier, thereby expediting the yellow-black phase transition in CsPbI3. We propose a general mechanism through which solvent molecules can greatly facilitate phase transitions that otherwise have prohibitively high transition energies.

Desulfurization Behavior of Magnetite Pellets Reduced by Isothermal Pure Hydrogen

The desulfurization behavior of magnetite pellets reduced by pure hydrogen at isothermal temperature is studied, the mechanism of self‐oxidation desulfurization is put forward, and the thermodynamic theoretical calculation and experimental verification of this mechanism are carried out. The feasibility of the reaction between iron sulfide and Fe3O4 is analyzed by HSC Chemistry 6.0 software. Additionally, a thermal gravimetric analyzer is used to further study the thermal behavior of pellet material under Ar atmosphere from 400 to 1400 K. The results show that the removal of sulfur in the isothermal reduction process of pure hydrogen does not depend on hydrogen phase diffusion and reduction temperature. During the heating process, self‐oxidation desulfurization occurs in the system, and the self‐desulfurization reaction is more inclined to Fe3O4 + FexSy → FeS + SO2. Under the experimental conditions, the temperature range of self‐oxidation desulfurization under conventional thermal field and microwave field is 700–1100 and 370–1140 K, respectively, and the desulfurization rate is 92.9% and 95.8%, respectively. The key to improving desulfurization by microwave radiation is that iron sulfide has good wave‐absorbing characteristics.

A Multilayer Nonlinear Permutation Framework and Its Demonstration in Lightweight Image Encryption

As information systems become more widespread, data security becomes increasingly important. While traditional encryption methods provide effective protection against unauthorized access, they often struggle with multimedia data like images and videos. This necessitates specialized image encryption approaches. With the rise of mobile and Internet of Things (IoT) devices, lightweight image encryption algorithms are crucial for resource-constrained environments. These algorithms have applications in various domains, including medical imaging and surveillance systems. However, the biggest challenge of lightweight algorithms is balancing strong security with limited hardware resources. This work introduces a novel nonlinear matrix permutation approach applicable to both confusion and diffusion phases in lightweight image encryption. The proposed method utilizes three different chaotic maps in harmony, namely a 2D Zaslavsky map, 1D Chebyshev map, and 1D logistic map, to generate number sequences for permutation and diffusion. Evaluation using various metrics confirms the method’s efficiency and its potential as a robust encryption framework. The proposed scheme was tested with 14 color images in the SIPI dataset. This approach achieves high performance by processing each image in just one iteration. The developed scheme offers a significant advantage over its alternatives, with an average NPCR of 99.6122, UACI of 33.4690, and information entropy of 7.9993 for 14 test images, with an average correlation value as low as 0.0006 and a vast key space of 2800. The evaluation results demonstrated that the proposed approach is a viable and effective alternative for lightweight image encryption.

Thermally-induced diffusion and structural phase transitions in Pt/Mn and Pt/Mn/Pt thin films

We demonstrate the possibility of diffusion formation of the chemically ordered L1 0-MnPt phase through the vacuum annealing of Pt(24 nm)/Mn(20 nm) and Pt(12 nm)/Mn(20 nm)/Pt(12 nm) layered stacks at 400 °C for 30 min. For the bi-layered stack annealed at 400 °C, the effect of Pt atoms segregation at the film/substrate interface was detected, which remained after annealing even at higher temperatures (500 °C and 600 °C) and prevented the whole homogenization of the chemical composition through the film depth. By contrast, for the tri-layered stack annealed at 400 °C, the presence of the additional Pt bottom layer enabled to change the rate and mechanism of reactive diffusion, leading to homogeneous distribution of components and enhanced crystallinity of the ordered L1 0-MnPt phase compared to the bi-layered sample. An explanation of the obtained experimental data is provided based on the fundamentals of mass transfer theory and its quantitative parameters (e.g. activation energy and diffusion coefficients).

Ultrahigh thermal stability and piezoelectricity of lead-free KNN-based texture piezoceramics

The contradiction between high piezoelectricity and uniquely poor temperature stability generated by polymorphic phase boundary is a huge obstacle to high-performance (K, Na)NbO3 -based ceramics entering the application market as Pb-based substitutes. We possess the phase boundary by mimicking Pb(Zr, Ti)O3’s morphotropic phase boundary structure via the synergistic optimization of diffusion phase boundary and crystal orientation in 0.94(Na0.56K0.44)NbO3−0.03Bi0.5Na0.5ZrO3−0.03(Bi0.5K0.5)HfO3 textured ceramics. As a result, a prominent comprehensive performance is obtained, including giant d33 of 550 ± 30 pC/N and ultrahigh temperature stability (d33 change rate less than 1.2% within 25-150 °C), representing a significant breakthrough in lead-free piezoceramics, even surpassing the Pb-based piezoelectric ceramics. Within the same temperature range, the d33 change rate of the commercial Pb(Zr, Ti)O3−5 ceramics is only about 10%, and more importantly, its d33 (~ 350 pC/N) is much lower than that of the (K, Na)NbO3-based ceramics in this work. This study demonstrates a strategy for constructing the phase boundary with MPB feature, settling the problem of temperature instability in (K, Na)NbO3-based ceramics.

Non-nematicity of the filamentary phase in systems of hard minor circular arcs.

This work further investigates an aspect of the phase behavior of hard circular arcs whose phase diagram has been recently calculated by Monte Carlo numerical simulations: the non-nematicity of the filamentary phase that hard minor circular arcs form. Both second-virial density-functional theory and further Monte Carlo numerical simulations find that the positional one-particle density function undulates in the direction transverse to the axes of the filaments while further Monte Carlo numerical simulations find that the mobility of the hard minor circular arcs across the filaments occurs via a mechanism reminiscent of the mechanism of diffusion in a smectic phase: the filamentary phase is not a {"modulated" ["splay(-bend)"]} nematic phase.

Modeling phase separation in solids beyond the classical nucleation theory: Application to FeCr.

Despite a large amount of work being devoted to study the phase separation in solids, the underlying physical mechanism responsible for such diffusive first-order phase transitions remains difficult to model outside the spinodal regime, i.e., in the nucleation and growth regime. This work presents an alternative of the classical nucleation theory for modeling phase separation in this regime, even for systems far from the solubility limit, i.e., for high degree of meta-stability where the classical nucleation theory does not hold. This method then allows a direct comparison between simulations and experiments always performed in solids with a high degree of meta-stability.

Effects of different gas energy shares on combustion and emission characteristics of compression ignition engine fueled with dual-fossil fuel and dual-biofuel

This study systematically investigates the energetic and environmental performance of a four-cylinder compression ignition (CI) engine fueled by gaseous and liquid dual-fuel (D-F), utilising various combinations of fossil fuels and biofuels. Fossil diesel or pure hydrotreated vegetable oil (HVO) – new generation biodiesel was used as the pilot fuel to initiate ignition of the gaseous fuel. The gaseous fuels used were natural gas (NG) and simulated biogas (BG) composed of 60 % NG and 40 % CO2 by volume, injected into the intake manifold at varying gas energy shares (GES) of 40 %, 60 %, and 80 %. Reference values were provided from conventional combustion of diesel fuel and HVO. This study used numerical simulations to examine indicators of combustion, such as ignition delay, premixed combustion phase, diffusion combustion phase, and subsequent combustion phases, across diverse fuel combinations. Within lean dual-fuel mixtures, when the gaseous fuel remained below the flammability threshold, the peak pressure was diminished, the rate of pressure rise was lowered, and the combustion process decelerated, facilitating a faster transition to the diffusion phase. As the engine load and GES increased, the excess air ratio decreased, bringing the air-fuel mixture closer to the flammability limit, which in turn altered the combustion characteristics and engine performance trends. Combustion with increasing BG content showed partial similarities to that of NG, though the high CO2 content in biogas was found to suppress combustion, functioning similarly to an exhaust gas recirculation. The study also compared brake thermal efficiency (BTE), as well as specific emissions of CO, HC, NOX, CO2, and smoke for the D-F engine operation against pure diesel and HVO at different loads and GES levels. Additionally, an overlimit function was used to assess the emission levels of D-F engines with reference to emission limits.

Effect of T’-YSZ@Al2O3 core-shell structure on fracture toughness of YSH24 ceramics

To meet the demands of higher operating temperatures in aero-engines, yttrium oxide fully stabilized cubic (C) phase hafnium oxide (YFSH) has emerged as a promising candidate for thermal barrier coatings due to its ultra-high melting and phase transition temperatures. However, its application is constrained by its inherently low fracture toughness. To enhance the fracture toughness of C-HfO2 phase ceramic, the metastable non-equilibrium tetragonal (T’) phase of Y0.08Zr0.92O1.96 (YSZ8) was synthesized using the sol-gel method. An Al2O3 layer was then coated on YSZ, forming a T’-YSZ@Al2O3 core-shell structure (with Al2O3 comprising 20 % of the YSZ volume). The phase organization stability and diffusion resistance of this T’-YSZ@Al2O3 core-shell structure were investigated. Composite ceramic bulks, with compositions x T’-YSZ@Al2O3/(1-x) YSH24 (where x is the volume fraction, x = 0, 0.1, 0.2, 0.3, 0.4), were prepared using spark plasma sintering (SPS). The impact of the T’-YSZ@Al2O3 addition on the fracture toughness of the YSH24 matrix and the toughening mechanisms were analyzed. The results indicate that the introduction of the T’-YSZ@Al2O3 core-shell structure with good structural integrity into YSH24 ceramics prevents phase transitions. As the volume fraction of the core-shell structure increases from x = 0–0.4, the fracture toughness initially rises and then decreases, reaching a maximum of 2.36 MPa·m1/2 at x = 0.3. This value represents a 38.8 % improvement compared to that of the single C-HfO2 phase YSH24 bulks. The primary toughening mechanism is attributed to the ferroelastic domain switching of T’-YSZ within the T’-YSZ@Al2O3 core-shell structure.

A numerical framework for modeling evaporation and combustion of isolated, spherically-symmetric, multi-component fuel droplets

This paper presents a comprehensive numerical framework for simulating the evaporation and combustion of isolated, spherically-symmetric, multi-component fuel droplets. The framework incorporates a detailed description of chemical reactions in the gaseous phase and is capable of modeling pure evaporation, autoignition, and hot-wire ignition scenarios.The transport equations for mass, species, and energy are solved in both the liquid (droplet) and gaseous (surrounding atmosphere) phases. Diffusion in the liquid phase is described using the Stefan–Maxwell theory, while in the gaseous phase, both molecular and thermal diffusion are considered. The model also includes the thermophoretic effect for carbonaceous particles and accounts for gas radiation through various models, ranging from optically-thin approximations to more complex methods like the P1 and discrete ordinate methods. Non-gray radiative effects are handled using the Weighted-Sum-of-Gray-Gases Model (WSGGM). Liquid/gas interface conditions are evaluated by imposing flux continuity of mass and energy, along with thermodynamic equilibrium for species. Deviations from ideal thermodynamic behavior in the liquid droplet are managed by incorporating a suitable activity coefficient or by using a proper cubic equation of state. Additionally, the presence of supporting fibers is modeled using a simplified one-dimensional approach. The transport equations are solved using the method of lines, with spatial discretization performed via the finite difference method on a body-fitted grid. The resulting system of Differential–Algebraic Equations (DAEs) is then solved using a fully-coupled approach.Thanks to its generality in terms of kinetic and thermodynamic descriptions and the reduced computational time, the proposed framework offers significant potential for advancing our understanding of the complex combustion processes of multi-component liquid fuels and for enhancing the planning and execution of experiments involving isolated fuel droplets.

Frequency stabilization of self-sustained oscillations in a sideband-driven electromechanical resonator

We present a method to stabilize the frequency of self-sustained vibrations in micromechanical and nanomechanical resonators. The method refers to a two-mode system with the vibrations at significantly different frequencies. The signal from one mode is used to control the other mode. In the experiment, self-sustained oscillations of micromechanical modes are excited by pumping at the blue-detuned sideband of the higher-frequency mode. Phase fluctuations of the two modes show near-perfect anticorrelation. They can be compensated in either of the modes by a stepwise change of the pump phase. The phase change of the controlled mode is proportional to the pump phase change, with the proportionality constant independent of the pump amplitude and frequency. This finding allows us to stabilize the phase of one mode against phase diffusion using the measured phase of the other mode. We demonstrate that phase fluctuations of either the high-frequency mode or the low-frequency mode can be significantly reduced. The results open new opportunities in generating stable vibrations in a broad frequency range via parametric down-conversion in nonlinear resonators. Published by the American Physical Society 2024

Unraveling the adsorption-limited hydrogen oxidation reaction at palladium surface via in situ electron microscopy

Palladium (Pd) catalysts have been extensively studied for the direct synthesis of H2O through the hydrogen oxidation reaction at ambient conditions. This heterogeneous catalytic reaction not only holds considerable practical significance but also serves as a classical model for investigating fundamental mechanisms, including adsorption and reactions between adsorbates. Nonetheless, the governing mechanisms and kinetics of its intermediate reaction stages under varying gas conditions remain elusive. This is attributed to the intricate interplay between adsorption, atomic diffusion, and concurrent phase transformation of catalyst. Herein, the Pd-catalyzed, water-forming hydrogen oxidation is studied in situ, to investigate intermediate reaction stages via gas cell transmission electron microscopy. The dynamic behaviors of water generation, associated with reversible palladium hydride formation, are captured in real time with a nanoscale spatial resolution. Our findings suggest that the hydrogen oxidation rate catalyzed by Pd is significantly affected by the sequence in which gases are introduced. Through direct evidence of electron diffraction and density functional theory calculation, we demonstrate that the hydrogen oxidation rate is limited by precursors' adsorption. These nanoscale insights help identify the optimal reaction conditions for Pd-catalyzed hydrogen oxidation, which has substantial implications for water production technologies. The developed understanding also advocates a broader exploration of analogous mechanisms in other metal-catalyzed reactions.

Toughening of a vacuum diffusion-bonded heterostructured AZ31/WE94/AZ31 alloy by interfacial reinforcement

Heterostructured materials have recently attracted extensive attentions from the materials community due to their superior combination of strength and ductility as compared to the conventional homogeneous counterparts. In the present study, the laminate AZ31/WE94/AZ31 Mg alloy was produced by vacuum diffusion bonding. The post annealing was carried out to improve the mechanical properties of the heterostructured Mg alloy. It is found the elemental diffusion and formation of interfacial phases enhance the interface bonding strength, thereby improving the comprehensive mechanical properties. The laminate sample annealed at 470 °C for 12 h shows a superior mechanical properties with a yield strength, ultimate tensile strength, and elongation of 158 MPa, 212 MPa and 12.9%, respectively. The higher annealing temperature leads to the growth of interfacial phase, which provides preferential nucleation sites for crack initiation and weakens the tensile properties.

Thermodynamic and Kinetic Properties of the Lithium-Silver System.

A carbon-silver anode has recently been shown to suppress dendrite formation in all-solid-state lithium-ion batteries. The role that silver plays in enabling the reversible deposition and stripping of lithium remains unknown. Furthermore, very little is known about the thermodynamic and kinetic properties of Li x Ag1-x alloys. Here, we report on an in-depth first-principles study of phase stability and diffusion mechanisms in the Li-Ag alloy system. We identify two new intermetallic phases that are predicted to be stable in Li-rich Li x Ag1-x alloys with stoichiometries of Li3Ag and Li11Ag2. Our calculations show that the peculiar and highly anharmonic energy surface of pure Li along the Bain and Burgers paths persists upon the addition of Ag to BCC Li. This has important implications for room-temperature phase stability and mechanical properties. We have also performed a systematic study of diffusion mechanisms in the Li x Ag1-x alloy system as a function of alloy concentration x. Diffusion in alloys and intermetallics is mediated by vacancies. High vacancy formation energies are predicted in the Li x Ag1-x alloy, especially in Ag-rich FCC solid solutions. Complex diffusion mechanisms are identified in the B2 and γ-brass intermetallic phases that include two-atom hops and second-nearest neighbor hops. The migration barriers are found to decrease with increasing Li concentration, with predictions of exceptionally low migration barriers of 0.1 eV in the D03 Li3Ag phase.

Exploring bonding temperature variations in diffusion brazing of B4C ceramics with Ni-Cr-Si-Fe-B interlayer: Mechanical and microstructural analysis

This study examines the impact of the bonding temperature parameter on the quality of diffusion brazing joints of B4C ceramics using a Ni-Cr-Si-Fe-B interlayer. Various factors including shear strength, hardness, microstructure, interfacial phenomena, elemental diffusion patterns, formed compounds and phases, and fracture surfaces of the samples were analyzed and compared. The brazed sample at 1110 °C for 1/2 h exhibited the highest shear strength of 62 MPa. Increase of the bonding temperature to the optimum level (1090–1110 °C) enhances the fluidity of the molten interlayer, facilitating its diffusion into the porosities of the ceramic components. This increase also promotes higher interactions within the system, creating favorable conditions for element diffusion. However, surpassing the optimum temperature (1110–1130 °C) may lead to increased destructive reactions and intensify the impact of the coefficient of thermal expansion (CTE) mismatch, resulting in residual stresses and a subsequent decrease in bond strength. The excessive increase in the bonding temperature (1130–1150 °C) can lead to the excessive fluidity of the molten interlayer, potentially causing effusion onto the joint's fixture and damaging the samples. The results indicate the formation of various compounds between the elements of the interlayer and carbon and boron elements, including SiC, Ni4B3, CrB2, Fe2B, Ni6Si2B, and B2Fe3Ni3, at the fracture surface of the sample bonded at 1110 °C. The more substantial peaks of these compounds, compared to other samples, could be a reason for the higher strength of this particular sample.

Morphology evolution and mechanism of massive three-level hierarchically porous silver fabricated by vapor phase dealloying

In this study, the Gasar process and vapor phase dealloying (VPD) method were combined to fabricate a massive three-level hierarchical porous silver (MTHPS), which composed of interconnected micron-sized, submicron-sized, and nanoporous structures. The key aspect of this study lies in the preparation of a hypoeutectic Gasar Mg91.6Ag8.4 alloy with the regular micron-scale pore structure as the dealloying precursor, improving the size of the hierarchical porous metal. Under high vacuum conditions, by adjusting the dealloying time and temperature, MTHPS samples with various morphologies were obtained. After dealloying, the MTHPS exhibited Gasar pores (diameter 376 ± 86 μm), submicron pores (diameter 465 ± 125 nm), and a continuous ligament/channel structure (pore size less than 70 ± 40 nm). The coarsening index was 3.6258, and the activation energy was measured to be 0.95 eV, indicating that the formation and coarsening of the pores during VPD are attributed to surface diffusion. The calculated evaporated mass of the precursor alloy after dealloying was very close to the experimental value (±0.004 g), indicating that the evaporation of Mg occurred simultaneously in both solid and liquid phases during the VPD process. This study elucidates the phase transformation characteristics, structural control, and diffusion mechanisms of MTHPS prepared by VPD, providing valuable insights for further research and applications of MTHPS.

Exploring W-EUROFER brazed joints: S/TEM and nanoindentation analysis following post-brazing tempering treatment

Tempering treatments are essential for restoring the hardness and microstructure of EUROFER steel when W-EUROFER joints are formed at temperatures exceeding the steel's austenitization point (890 °C). This post-brazing heat treatment can, however, alter the microstructure and thereby affect the mechanical properties. This study explores the microstructural and nanomechanical effects in the brazed area of W-EUROFER joints following this heat treatment, utilizing copper as an intermediate filler material. Using Scanning Transmission Electron Microscopy (STEM) with Energy Dispersive Spectroscopy (EDS) on FIB lamellae and nanoindentation techniques we examined the stability and phase characteristics of the post-tempered microstructure in two lamellae that covers the whole phases of the braze microstructure.The tempering process enhances copper diffusion and the growth of copper precipitates without significantly altering the joint's overall microstructure. Despite the general stress-relief effects of tempering, which typically lower mechanical properties, the diffusion phases formed during brazing maintained high hardness and modulus, indicative of a complex, element-rich composition. A reduction in mechanical properties was observed in the iron-rich phase near the W-braze interface and the EUROFER base material, aligning with the purpose of the heat treatment. However, the copper braze and tungsten base material largely retained their stability and resilience to thermal treatments.This research provides vital insights into the behavior of these material systems under thermal processing, highlighting the necessity of optimizing heat treatment parameters to preserve joint integrity in high-performance applications such as nuclear fusion reactors. The findings contribute significantly to the development of durable and reliable materials for fusion energy, emphasizing the importance of controlled tempering processes to enhance material properties.