Molten Phase Research Articles

Effect of current on the tribological behavior of Cu-Fe-P immiscible alloy produced by laser powder bed fusion

Cu-based immiscible alloys have significant potential application value in the field of electrical contacts. This study investigated the tribological behavior of Cu-Fe-P immiscible alloys produced via laser powder bed fusion (LPBF) under current-carrying conditions. The alloys consist of softer ε-Cu phase and harder Fe-rich phases. The Fe-rich phase acts as a protective reinforcement during current-carrying friction and wear tests, improving the wear resistance of the alloy. With the increasing current, the coefficient of friction initially rose and then decreased, whereas the wear rate showed a gradual increase. At low currents (0, 2, 3 and 5 A), mechanical wear predominantly governs the wear mechanism. As the current increases, the mechanical wear gradually transitions from adhesive wear to abrasive wear, accompanied by weak oxidative wear. At higher currents (7 A and 10 A), the wear mechanism is dominated by arc erosion wear and oxidative wear. Notably, when the current exceeded 2 A, an oxide film consisting of CuO, Fe2O3, and Fe3O4 formed, enhancing the frictional properties of the alloy. Once the current surpassed 5 A, the arc discharge occurred at high currents, forming molten phases and arc erosion pits on the worn surface of the Cu-Fe-P immiscible alloy.

Exact analytical solution of the equations for a quasiequilibrium two-phase domain: permeability and interdendritic spacing

This study is concerned with the theoretical description of a quasi-stationary process of directional crystallization of binary melts and solutions in the presence of a quasi-equilibrium two-phase region. The quasi-equilibrium process is ensured by the fact that the system supercooling is almost completely compensated by heat released during the phase transformation. Quasi-stationarity of the process determining constancy of the crystallization rate is ensured by given temperature gradients in the solid and liquid phases. The system of heat and mass transfer equations and boundary conditions to them under these assumptions is dependent on a single spatial variable in the reference frame moving with the crystallization rate relative to a laboratory coordinate system. Exact analytical solutions to the formulated problem in parametric form are obtained. The parameter of the solution is the solid phase fraction in a two-phase region. The distributions of temperature and impurity concentration in the solid, liquid and two-phase regions of the crystallizing system, the rate of solidification, and the spatial coordinate in the two-phase region depending on the solid phase fraction in it are found. An algebraic equation for the solid phase fraction at the interface between the solid material and the two-phase region is derived. Exact analytical solutions show that the impurity concentration in the two-phase layer increases as the solid phase fraction increases. Moreover, the solid phase fraction at the interface solid phase — two phase region and its thickness increase as the temperature gradient in the solid phase and the solidification rate increase. The developed theory allows us to determine analytically the permeability of the two-phase region and a characteristic interdendritic spacing in it. Analytical solutions show that the relative permeability in the two-phase region increases from a certain value at the interface with the solid phase to unity at the interface with the liquid phase. The selection theory of stable dendritic growth allows us to determine analytically a characteristic interdendritic distance in the two-phase layer that decreases as the temperature gradient in the solid phase increases. An increase of impurity in the molten phase gives a decrease in the interdendritic spacing within a two-phase region.

3D Printing of solvent-free PEO-Polyolefin solid polymer electrolyte by Fused Filament Fabrication

ABSTRACT 3D printing of energy storage systems is at the heart of In-Space Manufacturing strategy. Within this context, Li-ion polymer batteries printing through Fused Filament Fabrication (FFF) is envisaged. This study is devoted to optimising the extruded solid polymer electrolyte filament properties. As the poly(ethylene oxide) (PEO) – lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte offers the best Li+ conductivities but suffers from poor mechanical behaviour, poly(propylene) (PP) is added to ensure filament printability. An exhaustive investigation highlights the impact of the PEO molar weight and the LiTFSI and PP proportions. Fine-tuning these parameters alters molten phase viscosity, which affects the electrolyte morphology and ionic conductivity. Best formulations feature a co-continuous structure that provides effective mechanical reinforcement and exhibits the best ionic conductivity reported so far for an FFF-printed solvent-free polymer electrolyte of 1.2 × 10−4 S.cm−1 at 70°C. Therefore, it opens the way towards polymer battery printing, on the Earth and in microgravity conditions.

Novel anti-oxidation coating prepared by polymer-derived ceramic for harsh environments up to 1200 °C

Environmental barrier coatings (EBCs) are protective barriers that could prevent internal materials from oxygen and harmful agents. However, the combination between EBCs and polymer-derived ceramics (PDCs) is relatively hard but essential. In this work, an anti-oxidation coating based on PDCs is fabricated on target SiBCN ceramics by spraying. The coating reveals a uniform and continuous structure with an approximate thickness of 11.7 μm. Experiments and characterization such as oxidation, thermal shock, scratch, and electrical resistance tests were carried out to investigate the performance of coating. The results show that during the high-temperature oxidation process, the coating surface undergoes a molten phase transformation that effectively seals pores and cracks, preventing oxygen diffusion into the ceramic interior. Moreover, the coating can withstand 20 thermal shocks without failure, and firmly adheres to the substrate even after prolonged oxidation and repeated thermal cycling. Comparative analysis of temperature-resistance results demonstrates the efficacy of the coatings in protecting against oxidation up to 1200 °C. The developed PDC-EBCs here exhibit remarkable resistance to oxidation and thermal shock, along with high insulation resistivity. This strategy offers a straightforward and efficient solution for protecting electronic materials in harsh environments.

Ablation resistance of C/C–Hf1-xZrxC composites under an oxyacetylene flame at above 2700 °C

To the better application of C/C composites in thermal components of vehicles above 2700 °C, C/C–Hf1-xZrxC composites were prepared by CLVD, and the ablation behavior of composites was investigated. The results show that C/C–Hf0.5Zr0.5C has excellent ablation properties with linear and mass ablation rates of −0.23 μm/s and −0.31 mg/(s·cm2), respectively. ZrO2 molten phase and HfxZr1-xO2 particles are generated on the surface of C/C–Hf1-xZrxC composites during ablation. During the ablation process, defects are healed by the ZrO2 molten phase due to its mobility, which inhibits the diffusion of oxygen into the substrate. The ZrO2 molten phase is stabilized by the pinning effect of the HfxZr1-xO2 particles, which makes the ZrO2 molten phase better resistant to the scouring of the air stream. A relatively complete oxide layer is generated on the C/C–Hf0.5Zr0.5C surface, with a moderate amount of HfxZr1-xO2 exerting a pinning effect to hold the ZrO2 molten phase.

Valorization of oil‐based drilling cuttings as a substitute for bauxite in fracturing proppants application

AbstractThis study aimed to increase the scale of oil‐based drilling cuttings (OBDCs) resource utilization in the ceramic industry. The sintering process and mechanism were explored based on the analysis of physicochemical properties, phase transitions, and microstructure. The results showed that (1) The main ceramic‐technological characteristics of the OBDC were determined, which belonged to high‐silica solid waste with a high Si–Al ratio and a low acid–base ratio of oxides. (2) The low meltability temperature of the OBDC could largely influence the determination of the sintering temperature range for ceramic products. (3) The chemical components OBDC provided were involved in the formation of molten phases, which could affect dimensional accuracy and mechanical properties. Meanwhile, the dolomite promoted the formation of closed pores and enhanced lightweight performance. (4) Before 800°C, dolomite decomposed and reacted with SiO2 to form silicate, and then a new feldspar crystal appeared. After 1000°C, orthoclase completely melted into the molten phase, only two phases of quartz and diopside existed in the material until 1150°C. When the temperature was higher than 1350°C, the glass transition of the phase was basically intensified. (5) In the analyzed scenarios, the results indicated OBDC can only be doped in low contents and degrades the ceramic material properties.

Insight into the stabilization mechanism of Zn during co-gasification of sewage sludge and coal: Perspective of solid-liquid transition

In this study, the underlying mechanism of zinc (Zn) stabilization during the co-gasification of sewage sludge (SS) with Shenmu coal (SM) was investigated using an in-situ visual furnace to analyze the distribution of Zn species. The findings classified two distinct stages within the co-gasification process: the organic matter gasification stage, occurring below 1000 °C, and the inorganic mineral melting stage, occurring above 1000 °C. The addition of SM can extend the organic matter gasification phase, in which the porous carbon structure of the SM char aids in the capture of Zn released during the devolatilization of SS. However, a sustained reducing atmosphere promoted the formation of Fe3O4, causing Zn destabilization. Subsequently, during the inorganic mineral melting stage, the complete reaction of carbon released Zn, which was adsorbed onto the carbon surface. Furthermore, the ash from SM contributes to the melting of the co-gasification residues, enhancing Zn stabilization through encapsulation by the molten phase and stabilization within the spinel lattice. This study highlights the critical role of liquid encapsulation in Zn stabilization during co-gasification.

Calculation of liquidus in eutectic alkali halide mixtures using thermodynamic perturbation theory

A statistical-thermodynamic model that makes it possible to describe with good accuracy phase equilibria between melt and crystal in binary alkali halide mixtures with common cations and anions is proposed. This model is based on the thermodynamic perturbation theory, which takes into account the charge-dipole contribution to the interionic interaction of binary molten salts using a multicomponent mixture of charged hard spheres as a reference system. Specific expressions for chemical potentials, taking into account the charge-induced dipole interaction in the molten phase, are presented within the developed approach. Considering binary eutectic mixtures NaF–NaCl, CsF–CsCl, NaF–CsF, and NaCl–CsCl as an example, the liquidus curves obtained in two series of calculations are shown: with the equation of state and without it. The discrepancies between the calculated and experimental data on the position of eutectic equilibrium for most of the considered mixtures do not exceed about 10 percent on the temperature scale and 5 percent on the composition when using only the tabulated values of ionic radii and polarizabilities without any adjustment.

High Resolution Nanostructuring of Perovskites With Tunable Morphologies by Ultrafast Laser Direct Writing

AbstractMetal halide perovskites (MHPs) have attracted increasing attention in various optoelectronic devices due to their exceptional optical and electrical properties. The high precision patterning of MHPs is crucial adjective for device fabrication, while it is severely hindered by the active and sensitive chemistry of MHPs. In this work, high resolution and tunable nanostructuring of 2D MHP films are achieved by ultrafast laser direct writing (ULDW). The feature size of the created structure is down to 47 nm (λ/21), which is far beyond the diffraction limit of the optical system. The study proves the critical influence of the thermodynamic properties of materials on structure morphologies and establish a new mechanism of molten phase self‐evolution (MPSE) for the formation of super‐solution convex structures, which provides a new understanding for ultrafast laser‐matter interaction and high‐resolution patterning with ULDW. Different structure morphologies bring tunable optical properties. The applications are demonstrated in multimode information storage and encryption. The findings open new approaches to achieve hyperfine multi‐morphological structures on MHPs, which can boost many MHPs integration applications in nanophotonics, on‐chip electronics, and information encryption.

Exploration of laser ablation protection for HfC coatings on C/C composites above 2900K

Enhancing the laser ablation resistance of C/C composites is of paramount importance for their prospective application as thermal protection materials, given the rapid advancements in high-energy continuous laser technology. Herein, HfC coating was prepared by chemical vapor deposition (CVD) on the surface of C/C composites to resist the irradiation of high-energy continuous laser. The melting occurred with the formation of oxide products, and these molten phases accumulated at the edge of the ablation pit after laser ablation with two different powers. Furthermore, many cracks were formed around the ablation pit due to the formation of phase transformation stress during ablation. With the increase of laser power, the surface temperature and damage area of the coating increased, and the melting of oxide scale caused by ultra-high temperature was the main reason for the failure of coating. This work could be helpful to provide a theoretical basis for the design and application of laser protective coatings.

Versatile femtosecond laser interference patterning applied to high-precision nanostructuring of silicon

We present a high-precision nanostructuring technique based on beam interference from a commercial Ti:Sa femtosecond amplified laser (800 nm, 120 fs, 1 kHz, 1 mJ). Its potential and versatility is illustrated by applying the technique to the nanostructuring of silicon. Employing commercial and ad-hoc laser-fabricated diffractive optical elements together with standard optical components, periodic line gratings and spot arrays with tunable periods down to 650 nm can readily be fabricated. Moreover, fabrication of millimeter-size diffraction gratings via multipulse irradiation at processing speeds up to 0.5 mm/s is demonstrated. The variety of structures written in crystalline silicon feature amorphous fringes and dots with widths down to 300 nm. The corresponding complex topography profiles consist of surface elevations and depressions with sizes down to 120 nm that can be controlled by the laser fluence and fringe width, demonstrating the presence of several competing matter reorganization processes in the molten phase. The exceptional high-contrast ratio of the fringe intensity together with a near-Gaussian intensity envelope of the laser spot enable patterning with well-defined local fluences, paving the way for single-pulse fluence-dependent studies. The high-quality experimental data that can be obtained with this technique can prove critical for modelling attempts aimed at unravelling the underlying formation mechanisms of complex surface topographies in a wide range of materials. Furthermore, the technique presented here has outstanding potential for the rapid and versatile fabrication of high-precision metasurfaces.

MRI and PFG NMR studies of percolation effects in advanced melting during a cryoporometry characterisation of disordered mesoporous alumina

Cryoporometry (or thermoporometry) offers a way of pore structural characterisation for mesoporous materials that often needs little sample preparation, is relatively quick, and is statistically-representative for macroscopic samples. While it is well-known that freezing is controlled by pore-blocking, and is thus an invasion percolation process, the percolative nature of pore-to-pore co-operative advanced melting effects has been much less studied. In this work, PFG NMR studies, of diffusivity within the molten phase, have shown that the early melting process follows the scaling law, expected from percolation theory, below the percolation threshold. The percolation threshold thereby obtained was that for a 3D isotropic Poisson polyhedral lattice, consistent with the observation of patchwise macroscopic heterogeneities in the spatial distribution of local average pore size seen in MR relaxation time-weighted images. MRI has shown that once advanced melting effects kicked-in, around the percolation threshold, they occurred to different degrees in different slices along the length of the extrudate pellet. The macroscopic banding in pore-blocking, during freezing, and advanced melting effects, along the axis of the extrudate was consistent with anisotropic diffusional properties observed with MRI. Hence, it has been shown how the pore-pore co-operative effects can be utilised to improve structural characterisation of mesoporous solids.

Optical and Electrical Properties of A3[VS4] (A = Na, K) Synthesized via a Straightforward and Scalable Solid-State Method.

Two literature-known sulfido vanadates, Na3[VS4] and K3[VS4], were obtained through a straightforward and scalable synthetic method. Highly crystalline powders of both compounds were obtained from the homogeneous molten phases of starting materials via a─comparably rapid─solid-state technique. Low-temperature structure determination, ambient temperature powder diffraction, and solid-state NMR spectroscopy verify previous structural reports and indicate purity of the obtained samples. Both compounds show semiconductivity with the optical band gap values in the range of 2.1 to 2.3 eV. Experimental values of the ionic conductivity and dielectric constants are σ = 2.41·10-5 mS·cm-1, k = 76.52 and σ = 1.36·10-4 mS·cm-1, k = 103.67 at ambient temperature for Na3[VS4] and K3[VS4], respectively. It is demonstrated that Na3[VS4] depicts second-order nonlinear optical properties, i.e., second harmonic generation over a broad wavelength spectrum. The results introduce new aspects of sulfido vanadates as multifunctional candidates for potential optical and electrical applications.

Fabrication of high-permeance SiC filters reinforced with in situ-grown mullite whiskers for gas/solid filtration

The pursuit of cost-efficiency, superior strength, and excellent gas permeance has driven the development of silicon carbide (SiC) membranes or filters for gas/solid filtration. In this study, SiC filters with high gas permeance reinforced with in situ-grown mullite whiskers were successfully prepared through reaction bonding. Low-cost kaolin and bauxite were used as sintering aids and raw materials for mullite whisker formation, and MoO3 was used as an additive to promote mullite whisker growth. The effects of different sintering temperatures and the addition of kaolin, bauxite, and MoO3 on filter performance were systematically investigated. When the sintering aid and MoO3 content additions were 6 and 1.5 wt%, respectively, and the sintering temperature was 1450 °C, the resulting ceramic filter exhibited a porosity of 45.5 %, a bending strength of 17.9 MPa, and an average pore size of 47.7 µm. Moreover, the filter exhibited a high Darcy’s permeability coefficient of 2.42 × 10−11 m2, satisfactory chemical stability, and thermal shock resistance. The addition of MoO3 facilitated the consumption of the molten phases and increased the anisotropic growth rate of the mullite whiskers, which contributed to the fabrication of the high-permeance filters. Finally, the ceramic filters demonstrated good performance for the filtration of dusty gases loaded with fly ash particles with a mean size of 15.3 µm at room temperature and 300 °C, and the removal rate reached > 99.9 %. The pressure drop was a little lower than that of our commercially available SiC filters. The SiC filters showed good prospects in the field of gas/solid filtration.

Validation of the Wiedemann-Franz Law in Solid and Molten Tungsten above 2000K through Thermal Conductivity Measurements via Steady-State Temperature Differential Radiometry.

We measure the thermal conductivity of solid and molten tungsten using steady state temperature differential radiometry. We demonstrate that the thermal conductivity can be well described by application of Wiedemann-Franz law to electrical resistivity data, thus suggesting the validity of Wiedemann-Franz law to capture the electronic thermal conductivity of metals in their molten phase. We further support this conclusion using abinitio molecular dynamics simulations with a machine-learned potential. Our results show that at these high temperatures, the vibrational contribution to thermal conductivity is negligible compared to the electronic component.

Physicochemical transformation of gasification slags with different residue carbon contents during sintering/melting process

The ash residue after gasification in the coal gasifier contains a certain proportion of residual carbon, which exerts a significant effect on the slag properties such as sintering, melting, and flow within the furnace. The residues discharged outside the gasifier retain the distribution patterns of ash and residual carbon under gasification conditions. This study selected coarse and fine residues generated from an entrained-flow gasifier and investigated the transformation of slags with different carbon contents during heating process. The obtained ash residues underwent characterization to determine the modes of the compositions occurrence. Subsequently, ash residues with different carbon contents were observed for the sintering-melting processes with a high-temperature confocal scanning laser microscope (CSLM). With the aid of FactSage, the physicochemical transformation of slag particles was determined. The impact of residual carbon on particle characteristics manifests in both physical structure and chemical reactions. On one hand, residue residual carbon can act as a skeleton during the melting process, causing the molten phase to enter the pores of porous carbon, intensifying particle shrinkage. After the inorganic components melt, the liquid encapsulated by carbon retains the original particle shape. On the other hand, the carbon can react with the inorganic ash components. If the carbon content is less than 6%, a new FexSi with a high ash melting point can be formed. As the carbon content increases, the carbon reacts with the Si to form SiC. This implies a reduction in the liquid content. Therefore, the flow temperature is greatly delayed by an increase in carbon content above 14%.

High-Efficiency Thermal-Shock Resistance Enabled by Radiative Cooling and Latent Heat Storage.

Radiative cooling technology is well known for its subambient temperature cooling performance under sunlight radiation. However, the intrinsic maximum cooling power of radiative cooling limits the performance when the objects meet the thermal shock. Here, a dual-function strategy composed of radiative cooling and latent heat storage simultaneously enabling the efficient subambient cooling and high-efficiency thermal-shock resistance performance is proposed. The electrospinning and absorption-pressing methods are used to assemble the dual-function cooler. The high sunlight reflectivity and high mid-infrared emissivity of radiative film allow excellent subambient temperature of 5.1°C. When subjected the thermal shock, the dual-function cooler demonstrates a pinning effect of huge temperature drop of 39°C and stable low-temperature level by isothermal heat absorption compared with the traditional radiative cooler. The molten phase change materials provide the heat-time transfer effect by converting thermal-shock heat to the delayed preservation. This strategy paves a powerful way to protect the objects from thermal accumulation and high-temperature damage, expanding the applications of radiative cooling and latent heat storage technologies.

A novel rapid cooling assembly design in a high-pressure cubic press apparatus

In traditional high-pressure–temperature assembly design, priority has been given to temperature insulation and retention at high pressures. This limits the efficiency of cooling of samples at the end of experiments, with a negative impact on many studies in high-pressure Earth and planetary science. Inefficient cooling of experiments containing molten phases at high temperature leads to the formation of quench textures, which makes it impossible to quantify key compositional parameters of the original molten phase, such as their volatile contents. Here, we present a new low-cost experimental assembly for rapid cooling in a six-anvil cubic press. This assembly not only retains high heating efficiency and thermal insulation, but also enables a very high cooling rate (∼600 °C/s from 1900 °C to the glass transition temperature). Without using expensive materials or external modification of the press, the cooling rate in an assembly (∼600 °C/s) with cube lengths of 38.5 mm is about ten times faster than that in the traditional assembly (∼60 °C/s). Experiments yielding inhomogeneous quenched melt textures when the traditional assembly is used are shown to yield homogeneous silicate glass without quench textures when the rapid cooling assembly is used.

Mechanism of coupling corrosion caused by flue gas and deposits in municipal solid waste incinerator: Roles of H2O(g), HCl, and SO2

The key corrosive media and coupling corrosion mechanism in waste incinerators were investigated. The presence of H2O(g) and the fluctuation of HCl/SO2 concentration significantly affect corrosion by affecting chemical reactions rather than molten phase formation·H2O(g) had higher adsorption energy (−40.67 kJ/mol) on NaCl (100) surface than O2 (−7.95 kJ/mol), generating more HCl than Cl2 and inhibiting corrosion. Oxidation of HCl was catalyzed by alkali salts in waste incineration ash, enhancing the production of Cl2 by 110% and accelerating corrosion. SO2 participated in the sulfidation of NaCl/KCl to form Cl2 and increased the corrosion weight gain by about 1–2.5 times.

Investigation on barium zirconate nanocomposites for optical and dielectric properties

There are numerous applications for the barium zirconate (BaZrO3) perovskite. Regarding the molten phases created during the fabrication of copper-oxide-based superconducting single crystals, it exhibits high corrosion resistance. ZrO2 and BaZrO3 were created by the co-precipitation method in the current experiment. Powder X-ray diffraction, Fourier-transform infrared spectra, and energy dispersive analysis by X-ray, which displays the elemental analysis of the specimens, were used to analyze the samples. The majority of the particles were grouped together in this way. It must be useful in many catalytic processes due to its high ion exchange ability and redox moment and ferroelectric applications because of its high dielectric constant value.