Melt Structure Research Articles

Local structure and mobility in melts of ionic liquids-selected primary and secondary alcohols

We present the results of a systematic study of the influence of isomerism of selected primary and secondary alcohols on their processes of solvation in dimethylimidazolium (dmim+) chloride ionic liquids. The properties of this system are investigated near the melting temperature by means of the molecular dynamics method. The study of single particle tracking (SPT) trajectories plays a significant role in the present analysis of the features of the microscopic movement of molecules of the dissolved substance in the solution. We demonstrate that the isomerism of alcohol molecules in case of isobutanol and isopentanol leads to the increase of their self-diffusion coefficients due to the growth of the IL’s local structure near the solute as we move from the alcohol to its isomer. The motion of butanol/isobutanol and pentanol/isopentanol alcohols molecules in this process is determined both by the mass, and the hydrophobic properties of the solute. Conversely, we demonstrate that the motion of systems with propanol/isopropanol are determined by the structure of the solute.

Structure Models of Metal Melts: A Review

Nowadays, metallic materials are subject to increasingly high performance requirements, particularly in the context of energy efficiency and environmental sustainability, etc. Researchers typically target properties such as enhanced strength, hardness, and reduced weight, as well as superior physical and chemical characteristics, including electrochemical activity and catalytic efficiency. The structure of metal melts is essential for the design and synthesis of advanced metallic materials. Studies using high-temperature liquid X-ray diffraction (HTXRD) have established a broad consensus that short and medium range ordering exists within metallic melts. However, the high-temperature and liquid conditions during experiments obscure the fundamental physical characteristics, leading to ongoing discussions. Developing simplified models is a typical approach to deal with the complex systems, facilitating a clearer and more direct understanding of the underlying physical images. Here, different physical models of metal melts will be reviewed, starting with transient models, then following with thermodynamic statistical model. The physical image and applications of the models will be carefully discussed.

Melting, viscosity and structure of lithium-free CaO-SiO2 based melt: Substituting Li2O with Na2O and B2O3

Lithiation-free mold fluxes with excellent performances are urgently needed to be developed, due to the desire for Li2CO3 (Li2O) from the lithium battery industry. So, in this study, the melting, viscosity and structure of the CaO-SiO2 based flux melt, with the aim to replace Li2O by Na2O and B2O3, were investigated. Results show that the melting temperature decreased from 1258.1-1651.9 K to 1245.3–1632.5 K, and the viscosity at 1573 K decreased from 0.310 to 0.098 Pa s, when the ratio of Li2O/(Na2O + B2O3) decreased from 0.38 to 0.00. Meanwhile, the break temperature reduced from 1475.3 to 1451.4 K, and the activation energy of viscous flow also decreased from 181.44 to 55.39 kJ/mol, with the decease of Li2O/(Na2O + B2O3) ratio. Melt structure analyses indicate that the simpler structural units, such as Q0(Si), Q1(Si), [AlO4]5- tetrahedral and B-O- in [BO3] increased, while the more complex structural units, like Q2(Si), Q3(Si), bending vibration of Si-O-Al and boron ring in borate reduced, when Li2O was replaced by Na2O and B2O3. These changes suggest that the DOP of the flux melt was reduced and the melt structure was simplified during the lithiation-free process.

Boron diffusion, related isotope fractionation and the structural role of B in pegmatite forming melts

In this study, we experimentally investigate the diffusion of B in flux-rich (1.7 % Li2O, 2.5 % B2O3, 2.7 % P2O5 and 3.5 % F) pegmatite forming melts in order to assess the transport mechanisms of B in rare-element pegmatite deposits. Glasses were synthesized with either different B isotope compositions or with different B concentrations (up to 2.45 wt% B2O3). In order to explore the effect of water on transport properties, nominally dry and hydrous glasses (3.1–3.9 wt% H2O) were investigated. The produced glasses were combined to diffusion couples to study self-diffusion and chemical diffusion of B in the same chemical system. Experiments were conducted using an internally heated pressure vessel and a rapid-heat and rapid-quench cold-seal pressure vessel at 100 MPa Ar pressure in the temperature range of 850–1250 °C for 1.6–97.3 h. In chemical diffusion experiments, the flow of B is compensated by a combined opposing flow of all other cations and F, without changing their element ratios. Thus, effective binary diffusion coefficients are obtained. Similar activation energies were determined for B self-diffusion and chemical diffusion under nominally dry conditions (196 ± 6 kJ/mol and 200 ± 17kJ/mol, respectively). Many hydrous experiments show a tilted to strongly deformed interface after the run, which was probably formed by advective flow of the low-viscosity melts during heating under pressure. Based on the successful experiments, an activation energy of 138 ± 8 kJ/mol was estimated for chemical diffusion of B in hydrous melts. We show that B diffusivity correlates with the Eyring diffusivity and, therefore, with the melt viscosity. The stable isotopes of B fractionate kinetically along the diffusion profiles due to the faster diffusivity of 10B over 11B. This isotope fractionation can be quantified with an empirical isotope fractionation factor (β) of 0.032 ± 0.002. This effect is small, but significant and was previously not observed in experimental studies. While it is insensitive to the water contents used in our study, it seems to be strongly dependent on the experimental boundary conditions, such as the ratios of B between the diffusion couple halves and the B enrichment in the melt. Solid-state NMR experiments reveal that the majority of B is in trigonal coordination in our melts, which effectively weakens the melt structure. This further suggests that coordination differences are unlikely to be the driving force for B isotope fractionation between melt and fluid during late-stage fluid exsolution in pegmatitic systems.

Effect of BaO on viscosity and structure of B2O3–SiO2–Al2O3–Na2O–BaO glass lubricant

AbstractGlass lubricant with a suitable viscosity is critical for the efficient production of high‐quality titanium alloy in hot extrusion process. In this study, a new glass lubricant, (30.93‐0.309x)B2O3‐(48.45‐0.485x)SiO2‐(7.22‐0.072x)Al2O3‐(13.4‐0.134x)Na2O‐xBaO (BSANB), was proposed for titanium alloy hot extrusion. The effect of BaO content varying from 0 wt.% to 15 wt.% on its viscosity was investigated, and the mechanism of viscosity change was clarified through melt structure analysis by using molecular dynamics (MD) simulation, X‐ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The glass viscosity was measured in the temperature range of 950°C to 1100°C, and the atomic self‐diffusion coefficient of the glass melt was calculated. The results demonstrated that the BaO content has a significant influence on the viscosity of the BSANB glass at the hot extrusion temperature range. The viscosity value at 950°C was decreased by 52.87%, from 103.5 Pa·s to 48.8 Pa·s, when BaO content was increased from 0 wt.% to 15 wt.%. MD simulation results of the BSANB glass show that the self‐diffusion coefficient of Si atoms was lower than that of Al and B atoms, indicating that Si‐O bonds were more stable in the melt. The diffusion coefficient of Si atom was directly related to the rheological behavior of the melt, which can be reflected by the melt viscosity. The results of MD simulation, XPS and Raman spectral fitting at 950°C showed an increase in the amounts of Q1, Q0 and [BO4], while the amounts of Q2, Q3, Q4 and [AlO4] were decreased when BaO content was increased from 0 wt.% to 15 wt.%. This demonstrated that the melt network was depolymerized with an increased BaO content, which determined the melt viscosity change. In addition, the mechanism responsible for glass viscosity reduction due to temperature increase was also discussed.

Equation of State, Structure, and Transport Properties of Iron Hydride Melts at Planetary Interior Conditions

AbstractIron hydrides are a potentially dominant component of the metallic cores of planets, primarily because of hydrogen's ubiquity in the universe and affinity for iron. Using ab initio molecular dynamics, we examine iron hydrides with 0.1, 0.33, 0.5, and 0.6 mol fraction hydrogen up to 100 GPa between 3,000 and 5,000 K to describe how hydrogen content affects the melt structure, hydrogen speciation, equation of state (EOS), atomic diffusivity, and melt viscosity. We find that the addition of hydrogen decreases the average Fe–Fe coordination number and lengthens Fe–Fe bonds, while Fe–H coordination number increases. The pair distribution function of hydrogen at low pressure indicates the presence of molecular hydrogen. By tracking chemical speciation, we show that the amount of molecular hydrogen increases and the number of iron in Hx≥1Fey≥0 clusters decreases as the hydrogen concentration increases. We parameterize a pressure, volume, temperature, and composition EOS and show that the molar volume and Grüneisen parameter of the melts decrease while the compressibility and thermal expansivity increase as a function of hydrogen concentration. We find that hydrogen acts as a lubricant in the melts as the iron and hydrogen become more diffusive and the melts become more inviscid as the hydrogen concentration increases. We estimate 2.7 wt% hydrogen in the Martian core and 0.49–1.1 wt% hydrogen in Earth's outer core based on comparisons to seismic models, with the assumption that the cores are pure liquid iron‐hydrogen alloy, and we compare the small exoplanet population with mass‐radius curves of iron hydride planets.

Viscosity and structure correlation mechanism of Fe[sbnd]Cr[sbnd]C melt based on MD simulation

The viscosity of FeCCr melt affects the mass transfer behavior during steelmaking processes. Reasonable regulation of viscosity can improve production efficiency. There is a close relationship between melt viscosity and structure. Therefore, it is of great theoretical significance to analyze the correlation between viscosity and structure of chromium-containing iron melt for the optimization of the whole metallurgical process. This study experimentally investigated the viscosity of FeCCr melt and utilized molecular dynamics simulation to analyze the formation and growth behavior of atomic clusters, revealing the correlation mechanism between structure and viscosity. As the Cr content increased from 11 % to 13 %, the melt viscosity increased by 10.05 %. At a temperature range from 1773 K to 1473 K, the viscosity reached a maximum of 15.5 mPa·s, representing a 40.9 % increase. Simulation results indicated that CrC clusters within the melt act as intermediaries, connecting with CrFe and FeC clusters to form FeCrC clusters. The key influence of increased Cr content on viscosity lies in promoting the generation of FeCrC multicomponent clusters, while the key influence of temperature reduction lies in promoting cluster growth. With the increase in Cr content, the number of clusters at 1773 K increased from 154 to 175, and the average volume of clusters increased from 212 Å3 to 224 Å3. When the temperature decreased from 1773 K to 1473 K, the number of clusters increased by 51.2 %, and the average volume of clusters increased by 18.75 %. In comparison, the thermal state change had a greater impact on clusters, where temperature reduction led to rapid cluster growth, reduction of free volume within the melt, and ultimately resulted in increased viscosity due to the combined effects.

Multiscale Modeling of Vinyl-Addition Polynorbornenes: The Effect of Stereochemistry.

Vinyl-addition polynorbornenes are candidates for designing high-performance polymers due to unique characteristics, which include a high glass transition temperature associated with a rigid backbone. Recent studies have established that the processability and properties of these polymers can be fine-tuned by using targeted substitutions. However, synthesis with different catalysts results in materials with distinct properties, potentially due to the presence of various stereoisomers that are difficult to quantify experimentally. Herein, we develop all-atom models of polynorbornene oligomers based on classical force fields and density functional theory. To establish the relationship between chemical architecture, chain conformations, and melt structure, we perform detailed molecular dynamics simulations with the fine-tuned atomistic force field and propose simpler coarse-grained descriptions to address the high molecular weight limit. All-atom simulations of oligomers suggest high glass transition temperatures in the range of 550-600 K. In the melt state (800 K), meso chains form highly rigid extended coils (C∞≈11) with amorphous structural characteristics similar to the X-ray diffraction data observed in the literature. In contrast, simulations with racemo chains predict highly helical tubular chain conformations that could promote assembly into crystalline structures.

Multiple interaction electron beam powder bed fusion for controlling melt pool dynamics and improving surface quality

Low surface quality of fabricated parts and long processing times are two commonly stated reasons against a more wide-spread adoption of electron beam powder bed fusion (PBF-EB) as a commercially viable manufacturing technique. Aside from the large particle size distribution (45–150 µm) of processed powders, the surface roughness, limited structural resolution and process instabilities are attributed to unwanted dynamics of the melt pool, like spattering, balling, evaporation and melt pool displacement. As a result, a contouring step using slow but stable melting parameters is usually added to the process to improve surface quality, leading to increased processing times.In this study, we demonstrate how the surface quality can be improved by supplying the energy for melt pool formation over multiple, timely separated interactions. To investigate the effect of this multiple interaction processing (MIP), series of single line melt structures with increasing number of interactions were fabricated, characterized and corresponding thermal diffusion simulations performed. The experimental results show how MIP allows to lower surface roughness of melted structures through a reduction of spattering, balling and melt pool displacement during processing, while our simulation model identifies these benefits to be caused by a significant reduction in surface temperature and thus evaporation, with increasing number of interactions for melt pool formation. Our model further demonstrates, how a relatively simple, computationally inexpensive and thus scalable thermal diffusion model is capable of providing valuable information about thermal conditions during melt pool formation. Lastly, we introduce a few simple equations to calculate appropriate MIP parameters for any kind of scan strategy.

Mobility of Magmas Within the Earth: Insights From the Elasticity and Transport Properties of Hydrous Albitic Melts

AbstractThe continental crust is produced by the solidification of aluminosilicate‐rich magmas which are sourced from deep below the surface. Migration of the magma depends on the density (ρ) contrast to source rocks and the melt viscosity (η). At the surface, these silica‐rich melts are typically sluggish due to high η > 1,000 Pa s. Yet at their source regions, the melt properties are complexly influenced by pressure (P), temperature (T), and water contents (). In this study, we examined the combined P‐T‐ effects on the behavior of melts with an albite stoichiometry (NaAlSi3O8). We used first‐principles molecular dynamics simulations to examine anhydrous (0 wt % H2O) and hydrous (5 wt % H2O) melts. To constrain the P and T effects, we explored P ≤ 25 GPa across several isotherms between 2500 and 4000 K. The melts show anomalous P‐ρ relationships at low P ∼ 0 GPa and high T ≥ 2500 K, consistent with vaporization. At lithospheric conditions, melt ρ increases with compression and is well described by a finite‐strain formalism. Water lowers the melt density (ρhydrous < ρanhydrous) but increases the compressibility, that is, 1/Khydrous >1/Kanhydrous or Khydrous < Kanhydrous. We also find that the melt η decreases with pressure and then increases with further compression. Water decreases the viscosity (ηhydrous < ηanhydrous) by depolymerizing the melt structure. The ionic self‐diffusivities are increased by the presence of water. The decreased ρ and η by H2O increase the mobility of magma at crustal conditions, which could explain the rapid eruption and migration timescales for rhyolitic magmas as observed in the Chaitén volcano in Chile.

Relation between the viscosity and electrical conductivity of molten slag for coal gasification and their dependence on SiO2 content

Direct measurement of coal ash viscosity during coal gasification in slag-tapping gasifiers poses a considerable challenge. Molten slag with different viscosities (η) possesses various electrical conductivities (κ). This study explores the relation between η and κ as a potential method for evaluating slag viscosity during coal gasification. The role of SiO2, a major component in coal ash, in η and κ was clarified based on the characterization of structural units of aluminosilicates in the slag through Fourier transform infrared spectroscopy and Raman analysis. Results indicated that an increase in SiO2 addition caused a decrease of κ and an increase in the activation energies of both κ (Eκ) and η (Eη). In particular, when the addition was 2 %, η exhibited a fluctuation, and when the addition was 6 %, a decoupling was observed between η and κ. Such phenomena are intricately linked to the content of the SiO4 unit structure (Qn(Si)) and its polymerization degree within the melt structure, and η is less sensitive to structural alterations than κ.

Thermodynamic Assessment of the P2O5-Na2O and P2O5-MgO Systems.

Knowledge about the thermodynamic equilibria of the P2O5-Na2O and P2O5-MgO systems is very important for controlling the phosphorus content of steel materials in the process of steelmaking dephosphorization. The phase equilibrium and thermodynamic data of the P2O5-Na2O and P2O5-MgO systems were critically evaluated and re-assessed by the CALPHAD (CAlculation of PHAse Diagram) approach. The liquid phase was described by the ionic two-sublattice model for the first time with the formulas (Na+1)P(O-2, PO3-1, PO4-3, PO5/2)Q and (Mg+2)P(O-2, PO3-1, PO4-3, PO5/2)Q, respectively, and the selection of the species constituting the liquid phase was based on the structure of the phosphate melts. A new and improved self-consistent set of thermodynamic parameters for the P2O5-Na2O and P2O5-MgO systems was finally obtained, and the calculated phase diagram and thermodynamic properties exhibited excellent agreement with the experimental data. The difference in the phase composition of invariant reactions from the experimentally determined values reported in the literature is less than 0.9 mol.%. The present thermodynamic modeling contributes to constructing a multicomponent oxide thermodynamic database in the process of steelmaking dephosphorization.

Studying the features of complex beryllium-containing silicate phases co-crystallization in zonal samples using the x-ray electron probe microanalysis method

Research subject. Silicate ingots containing four species-forming components Be, Mg, Al, and Si and belonging to the crystallization region of beryllium indialite (with the formula of Mg2BeAl2Si6O18 and a beryl-type structure). Aim. To investigate the fundamental problem of identifying the patterns of matter differentiation and the stable and metastable phase formation in silicate matrices. Methods. The evolution of the phase composition of silicate melts was registered using a temperature gradient method. Results. New data on the features of phase transformations in silicate melts belonging to the region of beryllium indialite were obtained by electron probe microanalysis (EPMA). Co-existing metastable and stable mineral phases were identified, and the similarity of their compositions with different structures was shown. The nature of impurity phases at each stage of crystallization was established. Conclusions. The evolutionary sequence of phase associations ensuring the crystallization of beryllium indialite and metastable phases of a similar composition, the nature of which is determined by the initial ratio of components, was experimentally recorded. The range of possible phase associations that co-crystallize or replace a stable phase with a beryl structure in melts from the region of existence of beryllium indialite in the BeO–MgO–Al2O3–SiO2 system was extended. The selectivity of the coloring element chromium entry into various phases of the studied system is shown depending on the capabilities of their structure. The addition of a chromophore is a reliable criterion for visualizing successive layers, zones, and areas of changing phase associations in the final ingot.

Structure of TeO2 Glass and Melt by Reverse Monte Carlo Simulations of High-Energy X-Ray Diffraction Data Sets.

The short-range and medium-range structures of TeO2 glass and melt are elucidated by Reverse Monte Carlo (RMC) simulations of High-Energy X-ray Diffraction data sets published in an earlier study by Alderman et al. (J. Phys. Chem. Lett.11(1) (2020)427-431). The RMC analysis reveals that there exists a wide range of Te-O bond lengths in both TeO2 glass and melt short-range structures. The Te-O pair distribution function (PDF) of the melt has peaks centered at 1.87, 2.06, 2.35, 2.65, and 3.00 (±0.01) Å, whereas the corresponding peaks in the glass are at 1.91, 2.07, 2.28, 2.54, 2.77, and 3.00 (±0.01) Å. The Te-O partial PDF of the melt shows a peak at 2.35 Å, which is not present in the glass structure; therefore, the same co-ordination sphere radius of 2.36 Å cannot be used for calculating the Te-O co-ordination numbers in the TeO2 melt and glass, as done in the earlier study by Alderman et al. Using a more appropriate radius of 2.41 Å for glass and 2.22 Å for the melt, the corresponding Te-O co-ordination numbers are found to be 3.99 and 3.33, respectively. The RMC analysis successfully determined the O-O pair distributions, which show the first peaks at 2.31-2.33 (±0.01) Å. Finally, Te-Te pair distributions show peaks at slightly longer distances in the melt compared to those in glass, and the melt is found to have greater medium-range disorder.

Structure and Dynamics of THF Swollen Polystyrene Ionomer Melts

Structure and Dynamics of THF Swollen Polystyrene Ionomer Melts

The basic intermediate-range order structures in the FLiNaK–LaF3–Li2O melt: identification and characterisation

ABSTRACT In this paper, we investigate the structure of FLiNaK–LaF3 melt with small addition of Li2O through the theoretical approach combining ab initio molecular dynamics and simulation of the isolated structural units. The structure of the melt was studied in detail by calculation of radial distribution functions along with coordination numbers and radii. We found that oxyfluoride intermediate-range structure is formed in the melt. Our observations support the suggestions of other authors on formation of intermediate-range structures in fluoride melts containing metal oxides. Given structure shows long lifetime, the consideration of the isolated specie is valuable. We performed a simulation of ‘gas-phase’ [O2La4Fn] structure in order to calculate its Raman spectrum. It was found that the spectrum of the isolated structure agree in semi-quantitative manner with the vibrational density of states of the oxygen ions in the melt.

Widespread two-layered melt structure in the asthenosphere

Widespread two-layered melt structure in the asthenosphere

Explicating Electrical Conductivity and Melt Structure of the SiO2–MnO–TiO2 Welding Fluxes with Various MnO/TiO2 Mass Ratios

Explicating Electrical Conductivity and Melt Structure of the SiO2–MnO–TiO2 Welding Fluxes with Various MnO/TiO2 Mass Ratios

An Insight in the Viscosity–Temperature Property of CaO‐SiO2‐Al2O3‐Based Slag Systems from Melt Structure

Viscosity is an important property for CaO‐SiO2‐Al2O3‐based slag systems, which showcases different scenarios in basic and acid slag systems with temperature change. This article elucidates the mechanism of their difference in viscosity–temperature property from melt structure. Results reveal that basic slag shows a low degree of polymerization (DOP) and a low viscosity of the melt due to an excessive O2− ions depolymerizing the complex network structures, resulting in more low‐polymerized Q0(Si) units and less high‐polymerized Q3(Si) units. With the temperature decreases, the DOP and viscosity do not change significantly. However, the low DOP and viscosity favor crystal precipitation in the melt, leading to a solid–liquid mixed state of the slag, and thus a sharp increase in viscosity when the temperature decreases to 1275 °C. For acid slag, it undergoes a transformation into aluminosilicate structures with the introduction of numerous [AlO4]5− tetrahedra, accompanied by a significant increase in the relative mole fraction of high‐polymerized Q3(Si) units. Consequently, the DOP and viscosity are obviously higher than that of the basic slag. Furthermore, the DOP and viscosity of the acid slag increase continuously with the temperature decreasing, thus impeding crystal precipitation and enhancing the glass transition tendency of the molten slag.

Plutonium oxide melt structure and covalency.

Advances in nuclear power reactors include the use of mixed oxide fuel, containing uranium and plutonium oxides. The high-temperature behaviour and structure of PuO2-x above 1,800 K remain largely unexplored, and these conditions must be considered for reactor design and planning for the mitigation of severe accidents. Here, we measure the atomic structure of PuO2-x through the melting transition up to 3,000 ± 50 K using X-ray scattering of aerodynamically levitated and laser-beam-heated samples, with O/Pu ranging from 1.57 to 1.76. Liquid structural models consistent with the X-ray data are developed using machine-learned interatomic potentials and density functional theory. Molten PuO1.76 contains some degree of covalent Pu-O bonding, signalled by the degeneracy of Pu 5f and O 2p orbitals. The liquid is isomorphous with molten CeO1.75, demonstrating the latter as a non-radioactive, non-toxic, structural surrogate when differences in the oxidation potentials of Pu and Ce are accounted for. These characterizations provide essential constraints for modelling pertinent to reactor safety design.