Pure Melt Research Articles

Effect of Al Addition to Mg Melt on Microstructure of Mg-Ti Composites in Liquid Metal Dealloying Process

This study investigates the effect of adding Al to Mg molten metal on the microstructural characteristics and hardness of Mg-Ti composites fabricated via a liquid metal dealloying (LMD) process. The addition of Al to the Mg melt significantly reduces the dealloying rate of Cu in a Ti30Cu70 precursor during LMD. The rapid reaction of Al atoms with Ti results in the formation of a Ti3Al phase, which in turn inhibits the spinodal decomposition of Ti and Cu. This inhibition decreases the formation rate of α-Mg channels, thereby slowing down the dealloying process of Cu. As a result, as the Al content in the Mg melt increases from 0 to 3 to 6 wt%, the residual Cu content in the composite substantially increases from 0 to 42 wt%. The main phases comprising the composite change from Mg and Ti for the composite using a pure Mg melt to TixCuy, TixAly, and MgxCuy for the composites using Mg-Al melts. The hardnesses of the composites fabricated using the Mg-3Al and Mg-6Al melts are 344 and 354 Hv, respectively, which are more than twice that of the composite fabricated using the pure Mg melt (116 Hv). These results demonstrate that adding small amounts of Al to Mg melt considerably influences the dealloying behavior during LMD as well as the resultant microstructure and mechanical properties of the Mg-Ti composite.

Capillary interaction of copper melt with dense and porous MAX phase (Cr, Mn)2AlC

In the present work, we experimentally studied the interaction of a pure copper melt with a dense MAX-phase (Cr, Mn)2AlC after sintering by the electric pulse plasma method and a porous phase obtained by pressing at room temperature. The porous phase (20 % porosity) absorbs molten copper at temperatures above 1200 °C; the kinetics of absorption was directly measured using high-speed thermal and video cameras. The experiments were carried out in a vacuum of 10–3 Pa. Studies using scanning electron microscopy, EDX spectral analysis and X-ray diffraction have shown that a chemical interaction of the MAX-phase with a copper melt occurs with the formation of a solution of aluminum and chromium in copper and the decomposition of the MAX-phase to chromium carbides (stable or metastable). The dense, sintered sample also actively interacts with the melt, although the contact angles exceed 100°. The difference between porous and dense samples lies in the kinetics of interaction. The results were compared with experiments on wetting the Cr2AlC MAX-phase with a Cu (0.8 at.% Cr) melt conducted earlier. The described experimental conditions and the results of determining chemical and phase changes in the process of capillary interaction indicate the possibility of creating a composite material with a submicron structure of chromium carbide impregnated with aluminum bronze.

A novel strategy for modeling composition-/temperature-dependent viscosity in multicomponent melts: Mg-Al-Zn-Sn-Bi as a test case

A viscosity model based on CALPHAD principles, considering the influences of associates in multicomponent melts, was developed. A strategy for determining CALPHAD-type viscosity parameters in systems lacking experimental data was proposed, which combines the Kozlov-Romanov-Petrov model and thermodynamic descriptions. This model and strategy were applied to analyze viscosities in Mg-Al-Zn-Sn-Bi melts. The viscosity expressions of pure melts were initially assessed based on the available experimental data. Subsequently, the Arrhenius viscosities of Mg3Bi2, Mg2Sn, and MgZn2 associates were determined by integrating thermal-physical properties into Kaptay equation. Viscosity parameters for 10 sub-binary and sub-ternary systems within Mg-Al-Zn-Sn-Bi system were examined. A comparison between predicted and measured viscosities confirmed the accuracy of the model. Isothermal viscosities in all sub-ternary melts were calculated to assess the impact of alloying elements on viscosity. Additionally, viscosities in AZ91 alloys with Bi and Sn additions were predicted, demonstrating an increase in viscosity with higher Bi or Sn content.

Universality and nonuniversality in nonlinear shear rheology of entangled polystyrene solutions and melts with the same number of entanglements

The linear and nonlinear shear rheology of entangled polystyrene (PS) solutions diluted by styrene oligomers with various lengths was compared with the shear rheology of a pure melt having the same number of entanglements (Z) during startup shear and step-shear strain experiments using a cone partitioned-plate geometry. By fixing the same Z, the shear rheology of the PS solutions and the melt shows some universal features in the linear and nonlinear regimes. Undershoot of the shear stress growth coefficient is observed during the startup flow of the PS solutions and depends strongly on the length of the oligomers. The Rotation Zero Stretch model captures the stress overshoot and the steady shear viscosity quantitatively, except at the high shear rates when undershoot is observed. Stress relaxation after step-shear strain experiments reveals that the PS solutions show a transition from type A damping (close to the Doi–Edwards prediction) to type B (weaker than the Doi–Edwards prediction), while the pure melt having the same Z shows a type A response, which suggests that the length of the oligomers influences the nonlinear damping response. The nonuniversality of the nonlinear damping response of the solutions and the melt is possibly due to the changes in flow-induced friction reduction during step-shear strain deformation.

Numerical study and experimental validation of a porous biochar supported form stable composite for thermal energy storage

This study numerically investigates the performance of the melting process for a biochar-based phase change material latent heat energy storage system. The melting processes of a composite made from softwood biochar combined with paraffin RT28, were compared numerically using the equilibrium porous medium model in ANSYS Fluent. The set up was validated through results from previous literature and experimental work. The enhancement in melting was compared to the pure PCM melting scenario and the effects of different paraffins, boundary conditions and inclination angle were investigated for real world application. Softwood biochar composites significantly surpass the performance of paraffin alone, reducing the melting time by 79 %. Different paraffins within the softwood composite produced different melting times, ranging from 2565 s to 4790 s. In terms of inclination angle adjusting to 90° produced steadier heating and reduced the melting time by 63 % in the composite. These findings offer insights into optimising latent heat thermal energy storage systems for improved performance and reduced energy wastage, highlighting the potential of biochar composites in sustainable energy solutions.

Nonmonotonic Composition Dependence of Viscosity upon Adding Single-Chain Nanoparticles to Entangled Polymers.

Well-characterized single-chain nanoparticles (SCNPs), synthesized from a linear polystyrene precursor through an intramolecular [4 + 4] thermal cycloaddition cross-linking reaction in dilute conditions, were added to entangled polystyrene melts at different concentrations. Starting from the pure linear melt, which is much more viscous than the melt of SCNPs, the zero-shear viscosity increased upon the addition of nanoparticles and reached a maximum before eventually dropping to the value of the SCNP melt. Molecular simulations reveal the origin of this unexpected behavior, which is the interplay of the very different compositional dependences of the dynamics of the two components. The SCNPs become much slower than the linear chains as their concentration decreases because they are threaded by the linear chains, reaching a maximum viscosity which is higher than that of the linear chains at a fraction of about 20%. This behavior is akin to that of single-loop ring polymers when added to linear matrices. This finding provides insights into the design and use of SCNPs as effective entropic viscosity modifiers of polymers and contributes to the discussion of the physics of loopy structures.

On different implementations of boundary conditions in the meshless RBF-FD method for phase-field modelling of dendritic solidification

Dendritic morphology is one of the most common microstructures in solidifying metallic materials. The phase-field method represents one of the most suitable approaches for modelling the evolution of dendritic morphology. In this paper, the meshless RBF-FD method and forward Euler scheme are used to solve the partial differential equations arising from the phase-field model for dendritic growth. We consider the growth of a single dendrite into a supercooled pure melt. On the computational domain’s surfaces, we apply symmetric boundary conditions. Special care has to be taken in the RBF-FD method to satisfy boundary conditions accurately. In this paper, we test four different implementations of boundary conditions. In the first one, the boundary conditions are incorporated when constructing an interpolation problem in local support domains containing boundary nodes. In the second one, the interpolation problem in the local support domains does not consider boundary conditions, which are satisfied by solving a system of linear equations for values in all boundary nodes at each time step. The third one complements the second one with the use of ghost nodes. The fourth implementation is an alternative one, where the values in ghost nodes are determined by direct mirroring. The accuracy and computational efficiency of all four implementations are compared. We discuss the advantages and disadvantages of each implementation. We show that using ghost nodes is recommended for implementing Neumann boundary conditions in the RBF-FD method.

Kinetic properties of a dendrite tip in a supercooled melt of pure metal.

High-speed dendritic growth of a crystal from a deeply supercooled pure metal melt is considered. The dendrite tip growth equation serves as the basis of the study, while local nonequilibrium heat transfer prop- erties have also been taken into account. The regularities of melt supercooling influence on the curvature of the apex behaviour and heat removal from the solid phase have been obtained. The interval limits of crystal- lization phase boundary aperiodic stability are calculated. A standing wave of perturbation of the dendrite tip has been studied: the periods of oscillations in coordinate and time have been determined, as well as the pat- terns of their behavior when the wave attenuation parameter changes have been indicated. The results of a comparative analysis of the dendrite tip kinetic properties for nickel and copper are presented

Carbonate metasomatism in sub-continental lithospheric mantle: Insights from decoupled Nd[sbnd]Hf isotopes of Mesozoic gabbros in Jinan, eastern North China Craton

The ancient sub-continental lithospheric mantle (SCLM) of the eastern North China Craton (NCC) underwent metasomatism in the Triassic due to fluids derived from subducted Yangtze continental crust, followed by further metasomatism during the Jurassic–Cretaceous caused by fluids originating from subducted Paleo-Pacific oceanic slabs. However, the occurrence of carbonate metasomatism during these two geological events is a subject of debate, and the origin of carbonate-bearing metasomatic agents remains ambiguous. Here, we present an integrated study of petrography, whole-rock trace element data and Sr–Nd–Hf–Pb isotope data for the Jinan gabbros in the Luxi block of the eastern NCC. The Jinan gabbros show arc-like trace element patterns and enriched Sr–Nd–Hf–Pb isotopic compositions, suggesting that they originated from partial melting of the enriched ancient SCLM. In addition, there are remarkable similarities in Sr–Nd–Hf–Pb isotopes between the Jinan gabbros and HP–UHP metamorphic rocks in the Dabie–Sulu orogenic belt, indicating the involvement of continental crustal components from the subducted Yangtze block in the mantle source of the Jinan gabbros. The gabbro samples show decoupled NdHf isotopes with positive ∆εHf values (∆εHf = εHf – 1.55 × εNd – 1.21; Vervoort et al., 2011), which were mainly caused by a metasomatic agent with high Nd/Hf ratios. The increase in εNd values with increasing Hf/Hf* (Hf/Hf* = HfPM/[(NdPM × SmPM)0.5]) and Nb/La further indicates that the metasomatic agent in the mantle source was depleted in high field strength elements (HFSEs) but enriched in rare earth elements (REEs), resembling the mantle-derived carbonatites in the Luxi area. The Jinan gabbros show significant variations in εNd and εHf, which cannot be explained by the involvement of C–O–H fluids and pure carbonatitic melts in their mantle source. Instead, carbonate-bearing felsic melts from the deeply subducted Yangtze continental crust are proposed to have acted as metasomatic agents. Carbonate metasomatism can significantly weaken the strength and decrease the melting temperature of the overlying ancient SCLM. Therefore, carbonate metasomatism that occurred in the lithospheric mantle of the eastern NCC during the Triassic, likely associated with deep subduction of the Yangtze block, might have played a significant role in promoting lithospheric thinning and mafic magmatism in the late Mesozoic.

Granite magmatism and mantle filiation

Abstract. Current granite magma generation models essentially reduce to two groups: (1) intra-crustal melting and (2) basaltic origin. A mixed, crustal, and basaltic origin and therefore a mantle filiation has been proposed for most granite magma types. In contrast, strongly peraluminous silicic magmas such as two-mica leucogranites have been classically interpreted as products of pure crustal melting. In this paper, we re-examine this interpretation and the evidence for considering leucogranites as unique among granite types. In the first part, some key aspects of the intra-crustal melting model are reviewed. Classical assumptions are discussed, such as the use of migmatites to infer granite generation processes. Our knowledge of crustal melt production is still incomplete, and fluid-present H2O-undersaturated melting should be considered in addition to mica dehydration melting reactions. The source rock remains essential as a concept despite difficulties in the identification of source lithologies from their geochemical and mineralogical signatures. Incorporating spatial and temporal variability at the source and the possibility of external inputs (fluids, magmas) would represent useful evolutions of the model. Thermal considerations bring strong constraints on the intra-crustal melting model since the absence of mafic magmas reduces possible external heat sources for melting. In the second part, the origin of a strongly peraluminous silicic volcanic suite, the Macusani Volcanics (SE Peru), is detailed. Magmas were generated in a mid-crustal anatectic zone characterized by high temperatures and heat fluxes. Crustal metamorphic rocks (metapelites) were dominant in the source region, although Ba-, Sr- and La-rich calcic plagioclase cores and some biotite and sanidine compositions point to the involvement of a mantle component. The heat necessary for melting was supplied by mafic mainly potassic–ultrapotassic magmas which also partly mixed and hybridized with the crustal melts. The Macusani Volcanics provide an example of a crustal peraluminous silicic suite generated with a contribution from the mantle in the form of mafic magmas intruded in the source region. This, as well as the limitations of the intra-crustal melting model, establishes that a mantle filiation is possible for peraluminous leucogranites as for most other crustal (S-, I- and A-type) peraluminous and metaluminous granites. This stresses the critical importance of the mantle for granite generation and opens the way for unification of granite generation processes.

New insights into the mechanism of ultrasonic atomization for the production of metal powders in additive manufacturing

Ultrasonic atomization is one of the promising technologies for producing metal powders for additive manufacturing, where precise control of particle size and morphology is essential. In this study, we coupled an ultrasonic transducer with a carbon fiber plate and atomized liquid droplets and films under different vibration amplitudes. Water, glycerol, and pure aluminum melt were used to study the atomization mechanism and the resulting droplet/powder characteristics, respectively. High-speed optical and ultrafast synchrotron X-ray imaging were used to study in situ the ultrasonic atomization dynamics, including pulsation and clustering of cavities inside the liquid layer/films, development of capillary waves, and formation of liquid droplets. For the first time, we observed and captured the occurrence of cavitation during the atomization of resting drops, films and impact droplets. The inertial cavitation events interfered with the capillary waves across the interphase boundary, puncturing and breaking the boundary to produce atomized mist. The in situ observation revealed the intricate dynamics of ultrasonic atomization and underscored the pivotal role of cavitation events throughout the entire atomization process. We also conducted experiments on ultrasonic atomization of liquid aluminum, producing particles of perfectly spherical shape. The particle size tended to decrease with reduced vibration amplitude Our work has demonstrated the important processing strategies on how to tailor the particle size while ensuring consistent particle shape and morphology, which is the key processing capability for producing high quality powders for additive manufacturing applications.

Formation behavior of Fe–Zn intermetallic layers at the interface between Fe–Mn and pure Zn melt at 460°C

Formation behavior of Fe–Zn intermetallic layers at the interface between Fe–Mn and pure Zn melt at 460°C

Ab initio molecular dynamics study of the local structures and migration behaviors of liquid Sb-based alloys

High-purity Sb is widely applied in the semiconductor industry, infrared detection and non-volatile memory. An in-depth knowledge of the local structure and related properties in liquid Sb-based alloys proves to be highly advantageous in the purification of Sb. In this work, an ab initio molecular dynamics simulation was used to study the local structures, dynamical properties, electronic structures and migration behaviors of liquid X-containing (X = As, Bi, Cu, Fe) Sb-based alloys. Among these solute atoms, the distribution coefficient of As/Bi is much larger than that of Cu/Fe. The results showed that the local structures around As/Bi are looser than those around Cu/Fe. The local structure around As/Bi contains a higher fraction of low-index bond pairs than that around Cu/Fe, and its local topological order of triples is closer to pure Sb melt. The coordination polyhedrons using As/Bi as the centered atom have more relaxed short-range order clusters than those using Cu/Fe as the centered atom. Different local structures and chemical effects may lead to different migration behaviors of solute atoms in the Sb melt.

Thermodynamic modelling of continental arc-adjacent magmatism: the Loicas Trough, N. Patagonia, Argentina

Continental arcs are associated with volcanism concentrated into two main belts—the main arc and back arc, often separated by fold and thrust belts. The Loicas Trough, Argentina, is a post-orogenic extensional feature that obliquely cuts the fold and thrust belts. The trough hosts large Pliocene–Holocene volcanic centres, including Domuyo and Tromen, that lie between the main arc and back arc and thus provide a rare window into this setting. We present major and trace element data for the Loicas Trough, which we combine with geochemical modelling using the Magma Chamber Simulator (MCS) to explore the origin and evolution of the volcanism. The lavas display a wide continuous range from alkaline basalts to subalkaline rhyolites. Trace elements reveal variable extents of arc enrichment (2 < Nb/U < 28), which correlate with proximity to the trench and differentiation indices. Our results and MCS models indicate that the Loicas Trough parental magmas formed from compositionally zoned mantle. Best-fit models indicate that the differentiation occurs at middle and upper crustal levels, in sharp contrast to lower crustal hot zones beneath main arcs. Assimilation of partial crustal melts drives compositional evolution and obscures source signatures. Pure or high fraction end-member partial crustal melts are also identified at Domuyo based on their low Ba (~ 250 ppm) and moderate Sc contents (~ 8 ppm). We find evidence of similar lavas in transtensional settings adjacent to continental arcs worldwide, which do not adhere to the main versus back arc volcanism binary. We suggest the term arc-adjacent magmatism, where compositions are mainly controlled by extensive assimilation and reworking in the middle to upper crust.

Змочування та контактна взаємодія напівпровідникових оксидних матеріалів Ga2O3, In2O3, ZnO з металічними розплавами у вакуумі

Semiconductor oxide materials such as gallium, indium and zinc oxides play an important role in a development and production of a variety of electronic devices. Experimental studies of these materials allow to define, for example energetic or other physical parameters of the devices created and also to improve existing technologies of their production, metallization and joining of electrocontacts by way of brazing which require additional wetting studies. It should be noted that data on wetting of mentioned oxides by metals are practically absent in literature. Thus a detailed experimental study of the interfacial interaction, adhesion and wetting of Ga2O3, In2O3 and ZnO oxide materials with some pure metal melts (Ga, In, Sn, Au,Ge, Ag, Cu) in vacuum was performed by the sessile drop method using photo- and video- fixing including temporal and temperature dependencies of contact angles. It was found that pure metals don't wet powdery pressed specimens of Ga and In oxides in the temperature range studied and vary in a rather narrow range. For ZnO system the significant effect of experiment temperature and hold-up time on the values of contact angles for some metals (Ga, Ge, Sn, Cu) is observed. For example wetting angles for Ga change from above 90 degrees at low temperatures up to 49 and full spreading at 1173⎯1373 K. This effect may be attributed to the activation of chemical reactions, change of oxide stabilities at high temperatures at the interface. Last metals can be used as adhesive-active additions to base brazing alloy. Keywords: gallium, indium, zinc oxides, semiconductor, wetting, contact interaction, metal melt.

Cooling rate calculation of pure aluminum solidified during a novel gas-assisted continuous casting and extrusion process

Gas-assisted continuous casting and extrusion (GAC) process is a novel technique for the continuous preparation of non-equilibrium solidified materials. To evaluate the solidification rate of the melt during GAC, the cooling rate of pure aluminum melt solidified in the wheel groove is calculated, based on the Newtonian heat transfer model and the one-dimensional Fourier heat transfer model. Results show that the cooling rate of the melt during GAC mainly depends on the conduction heat transfer in the wheel groove and the melt thickness. When the thickness of the pure aluminum melt is between 1 and 2.5 mm, the cooling rate can reach 103–104 K s−1, which is much higher than that in CAXTEX (~10 K s−1). It means that GAC is a very effective process in the preparation of non-equilibrium solidification alloys.

Defying decomposition: the curious case of choline chloride

Chemists aim to meet modern sustainability, health, and safety requirements by replacing conventional solvents with deep eutectic solvents (DESs). Through large melting point depressions, DESs may incorporate renewable solids in task-specific liquids. Yet, DES design is complicated by complex molecular interactions and a lack of comprehensive property databases. Even measuring pure component melting properties can be challenging, due to decomposition before melting. Here we overcame the decomposition of the quintessential DES constituent, choline chloride (ChCl). We measured its enthalpy of fusion (13.8 ± 3.0 kJ ⋅ mol) and melting point (687 ± 9 K) by fast scanning calorimetry combined with micro-XRD and high-speed optical microscopy. Our thermodynamically coherent fusion properties identify ChCl as an ionic plastic crystal and demonstrate negative deviations from ideal mixing for ChCl—contradicting previous assumptions. We hypothesise that the plastic crystal nature of ammonium salts governs their resilience to melting; pure or mixed. We show that DESs based on ionic plastic crystals can profit from (1) a low enthalpy of fusion and (2) favourable mixing. Both depress the melting point and can be altered through ion selection. Ionic plastic crystal-based DESs thus offer a platform for task-specific liquids at a broad range of temperatures and compositions.

Exploration of phase change material melt front during latent heat thermal energy storage charging

Latent Heat Thermal Energy Storage (LHTES) is a technology that utilises the phase change energy of a material to store energy and is used in multiple engineering disciplines. The use of this technology at high temperatures presents new material challenges that need to be considered. The exploration of Phase Change Material (PCMs) melting phenomena was completed with finite volume methods to model advection-diffusion interactions of different PCM classes undergoing pure substance melting. This study modelled a two-dimensional system with heat flux elicited by an isothermal wall – producing a melt front in the PCM. The investigation focussed on retention of a Solid Salt Barrier (SSB) between the liquid PCM and the storage tank wall. The importance of such a barrier is to mitigate the corrosion between the liquid PCM and the containment vessel. Results reveal the possibility of SSB retention through the adaptation of a LHTES system aspect ratio. A thermal storage inefficiency via unmelted PCM has been demonstrated and quantified when an SSB is maintained. Through varying geometry and PCM choice (carbonate, fluoride, and chloride eutectics), it was also shown that SSB retention is possible; however, when optimising the rate of internal enthalpy change, the corresponding aspect causes the SSB protected wall to be insignificant compared to exposed surfaces at the top and base. This paper provides insight into the implications of aspect ratio choice for thermal energy storage tank designs; as well, suggestions are made regarding exploration of divergent geometries to greater utilise the PCM energy storage capacity available in SSB systems.

Numerical simulation of pure metal melting and solidification with coupled multiphysics analysis

Numerical modeling of the melting and solidification process is a complex phenomenon. It involves the coupling of various physics, such as thermal, structural & fluid flow. This article examines the solidifying of structural steel metal simulated by coupled thermal, structural, and fluid flow physics was taken in to account and run in COMSOL Multiphysics software. In this present study, both solid and fluid phases are taken in a single domain and separated with a fusion temperature boundary. With the help of Stefan energy balance condition, the moving front (interface boundary of solid & liquid region) through time is calculated. A coupled heat transfer and laminar flow distribution and phase transition by a moving boundary interface were considered. Later, structural analysis is coupled with the study of stress distribution. Numerical modeling of transient coupled multiphysics is used for investigating the thermal distribution, velocity profiles, and stress distributions during the solidification process.

Redefined interface error, 2D verification and validation for pure solid-gallium phase change modeling by enthalpy-porosity methodology

For simulating phase change process of pure solid gallium, previously published literature contains some key problems, including the inappropriate definition & computation for interface errors, and the unsatisfactory numerical verifications & validations. Herein, the 2D verifications and 2D validations for the enthalpy-porosity modeling of pure gallium melting starting from a vertical end wall have been reported comprehensively. The well-known and classic experimental data presented in literature are used to verify and validate the model. The groundbreaking contributions in this work are that: i) The definition and computational method of the interface-position errors between the numerical and experimental results are revisited and proven carefully; ii) The numerical schemes as well as major parameters of 2D modeling gallium melting are selected with overall interface error <9%. However, these schemes and parameters are not appropriate for the solidification modeling of gallium due to the irregular and non-reproducible interface shapes caused by highly anisotropic properties of solid crystal gallium as experimentally reported in literature; iii) The 2D validations of enthalpy-porosity modeling of gallium melting are investigated in detail, and the maximum interface error is within the limits of ±12%. Moreover, the simulated liquid volume fractions and dimensionless heat transfer coefficients are well correlated in terms of related criteria parameters, and they are compared with correlations available in literature. It is concluded that to solidly validate the modeling of pure metal melting, both the global parameters (e.g., volume-averaged liquid fraction) and the local parameters (e.g., interface position) need to be considered together.