Mechanisms of the Origin of Fine and Non-Dendritic Grains at the Sonotrode–Liquid Metal Interface During Ultrasonic Solidification of Metals

Proposed grain refinement mechanisms during ultrasonic solidification have been explained in terms of refinement between cavitation enhanced nucleation and fragmentation of dendrites according to the casting conditions. Solidification studies also describe the activation of nucleation under pressure pulses after bubble implosion as an additional supporting mechanism for grain refinement. This study clarifies some overlooked concepts and proposes a plausible grain refinement mechanism explaining the role of cavitation in pure Zn and a Mg–6 wt pct Zn alloy. Equivalent grain size and grain density have been obtained in pure Zn and the Mg–6 wt pct Zn alloy (grain size distribution ranging from 40 to 200 µm) when UST was applied after the onset of solidification. These fine, non-dendritic grains originate from the cavitation zone beneath the sonotrode. Significant thermal undercooling surrounding the low superheat sonotrode in contact with the melt is responsible for the formation of a solidified layer (typically the thickness is equivalent to the average grain diameter) at the sonotrode–melt interface. High-frequency vibrations with or without cavitation at this interface assist the separation of these fine grains, which are then carried into the melt by acoustic streaming. A possible mechanism for the separation of fine grains produced from the cavitation zone is explained with the help of established concepts reported for the ultrasonic atomization process.

     

Review of Microstructure Evolution in Hypereutectic Al–Si Alloys and its Effect on Wear Properties

Al–Si alloys with silicon content more than 13 % are termed as hypereutectic alloys. In recent years, these alloys have drawn the attention of researchers due to their ability to replace cast iron parts in the transportation industry. The properties of the hypereutectic alloy are greatly dependent on the morphology, size and distribution of primary silicon crystals in the alloy. Mechanical properties of the hypereutectic Al–Si alloy can be improved by the simultaneous refinement and modification of the primary and eutectic silicon and by controlling the solidification parameters. In this paper, the effect of solidification rate and melt treatment on the evolution of microstructure in hypereutectic Al–Si alloys are reviewed. Different types of primary silicon morphology and the conditions for its nucleation and growth are explained. The paper discusses the effect of refinement/modification treatments on the microstructure and properties of the hypereutectic Al-Si alloy. The importance and effect of processing variables and phosphorus refinement on the silicon morphology and wear properties of the alloy is highlighted.     

Influence of Phosphorus on the Nucleation of Eutectic Silicon in Al-Si Alloys

The role of phosphorus (P) in the heterogeneous nucleation of eutectic silicon (Si) and the evolution of eutectic grains in hypoeutectic aluminum-silicon alloys were investigated. Systematic additions of P in the range of 0.5 to 20 ppm to Al-7 wt pct Si alloys of different purities have shown that the morphology of the eutectic Si changes from a fine plate- to a coarse flake-like structure. The growth of eutectic grains was investigated by interrupting the eutectic reaction by quenching experiments. Moreover, the macroscopic growth mode of the eutectic grains was characterized by electron backscatter diffraction. An increase in P concentration from 2 to 3 ppm resulted in a transition of the macroscopic growth mode of the Al-Si eutectic in high purity alloys from growth with a planar front with a strong dependence of the thermal gradient, to nucleation in the vicinity of the primary Al dendrites and subsequent growth of distinct eutectic grains. It is suggested that AlP particles are the key impurities acting as potential nucleation sites for eutectic Si. This is further substantiated as with increasing P concentration nucleation and growth of the Al-Si occurred at higher temperatures close the equilibrium Al-Si eutectic solidification temperature at 850 K (577 °C). In addition, the recalescence undercooling ΔT _R,eu was reduced from 4.5 K (0.5 ppm P) to 1.5 K (20 ppm P) in high purity alloys. This was accompanied by a drastic increase of the nucleation rate of the eutectic grains.     

Solidification behavior,microstructure and silicon twinning of Al-10Si alloys with ytterbium addition

The solidification behavior, micro structure and silicon twinning of Al-10 Si alloys with Yb addition were investigated by thermal analysis, optical microscopy, X-ray diffraction. scanning electron microscopy, and transmission electron microscopy. The results indicate that the nucleation temperature, minimum temperature, and growth temperature of Al-lOSi alloys decrease with increasing Yb content. The cooling curves of the Yb-modified alloys exhibit marked recalescence. The recalescence of the modified alloy peaks at 2.3 ℃ when the Yb content is 0.7 wt%. The 3 D morphologies of eutectic Si in Yb-modified alloys change from a coarse plate-like structure to a honeycomb structure with many fine fibrous structures.The Al-Si-Yb intermetallic compound is observed in the 1.0 wt% Yb-modified alloy. Meanwhile, XRD analysis and TEM results indicate that the average twin spacing in the Yb-modified alloys is 18-46.2 nm.The average twin spacing of eutectic Si decreases with increasing Yb content. When the Yb content in the modified alloy is increased to 0.7 wt%, the average twin spacing value of eutectic Si reaches to 18 nm,which promotes the formation of twins and refinement of eutectic Si.     

Computer Aided Cooling Curve Analysis and Microstructure of Cerium Added Hypereutectic Al–Si (LM29) Alloy

Thermal analysis of LM29 alloy and Ce added LM29 alloys was carried out. The effect of cerium addition on solidification parameters and microstructural features of hypereutectic Al-Si (LM29) alloy was studied using Newtonian analysis technique. Thermal analysis parameters such as primary and eutectic phase nucleation and solidus temperatures were determined. The addition of Ce to LM29 alloy decreased the nucleation temperature of primary silicon and eutectic silicon. The microstructural examination of Ce added LM29 alloys revealed the presence of a polyhedral shaped Al–Si–Ce compound that might have caused the refinement of primary and eutectic silicon. The dendrite coherency point temperature of LM29 alloy was found to be suppressed on addition of Ce.     

Effect of Cooling Rate and Neodymium Addition on Beta Intermetallic Phase of Al–Fe–Si Ternary System

Aluminium silicon alloys are widely used in automotive industry and other structural application. However, the presence of high content of iron element in Al–Si alloys lead to precipitation of beta intermetallic phase that has a detrimental effect on mechanical properties. Reducing the adverse effects of β-Al₉Fe₂Si₂ precipitates can be achieved by altering their morphology by adding element modifier and increasing solidification cooling rate. In this present work, simultaneous thermal analysis was used to study the effect of cooling rate (5, 10 and 30 °C min^?1) on beta phase formation in Al–7Si–1Fe alloy added with neodymium at 0.3, 0.6 and 1 wt%. The beta phase precipitates were then characterized using optical microscopy and scanning electron microscopy equipped with EDS. Image analysis results showed the reduction in size of beta intermetallic phase as a result of the rare earth addition. Further analysis also showed the refinement of eutectic silicon.     

Microstructure and Properties of Fe–Cr–B–Al Alloy After Heat Treatment

By means of optical microscope, scanning electron microscope, X-ray diffraction, energy dispersive spectrometer, Rockwell and Vickers hardness tester, and wear tester, the microstructure and properties of Fe–10Cr–1B–4Al alloy quenched in different temperature has been studied. The results show that the microstructure of as-cast Fe–10Cr–1B–4Al are composed of pearlite, ferrite and the eutectic borocarbide which shows a network distribution along grain boundaries. The eutectic borocarbides are composed of M₇(C, B)₃, M₂(B, C) and M₂₃(C, B)₆. As the quenching temperature increases, the network structure of eutectic borocarbide breaks, but the type of eutectic borocarbide has no obvious change, and the matrix structure changes gradually from ferrite to pearlite. As the quenching temperature increases, the macro-hardness and the matrix micro-hardness of Fe–10Cr–1B–4Al alloy increases gradually. The macro-hardness and matrix micro-hardness of alloy reach the highest value of 45.7 HRC and 388.1 HV, respectively when the quenching temperature is 1150 °C. The hardness of alloy decreases slightly when the quenching temperature is too high. While quenching at 1150 °C, the alloy has the highest wear resistance and good comprehensive properties.     

Microstructures of Al–Cu–Ag Ternary Eutectics Under Near-Isothermal Conditions

The three-phase eutectic microstructures in Al–Cu–Ag ternary alloys are complex and only directional solidification (DS) structures have been systematically studied in the literature. In order to better understand the large variation of eutectic structures in this system, three off-eutectic alloys in the vicinity of the nonvariant eutectic composition were solidified in a differential scanning calorimeter (DSC). The DSC was operated between 450 and 550 °C and at a heating and cooling rate of 1 °C/min to produce near-isothermal conditions. The intermetallic phase ζ-Ag₂Al is found to behave like pure metallic phase and forms primary dendrites. The ζ-Ag₂Al phase has a regular morphology in eutectics, while the θ-Al₂Cu exhibits big anisotropy of intermetallic nature and shows elongated morphology in the unconstraint grown eutectics. Three basic eutectic structures are categorized based on the relative phase arrangement: (1) semi-regular eutectic with elongated θ-Al₂Cu; (2) regular eutectic with rod-like ζ-Ag₂Al embedded in θ-Al₂Cu and (3) irregular eutectic with θ-Al₂Cu in ζ-Ag₂Al. They have nearly the same phase fraction and composition but distinct phase size distribution. The DSC eutectic structures are compared with reported DS eutectic structures.     

Refinement of Eutectic Si Phase in Al-5Si Alloys with Yb Additions

A series of Al-5 wt pct Si alloys with Yb additions (up to 6100 ppm) have been investigated using thermal analysis and multiscale microstructure characterization techniques. The addition of Yb was found to cause no modification effect to a fibrous morphology involving Si twinning; however, a refined plate-like eutectic structure was observed. The Al₂Si₂Yb phase was observed with Yb addition level of more than 1000 ppm. Within the eutectic Al and Si phases, the Al₂Si₂Yb phase was also found as a precipitation from the remained liquid. No Yb was detected in the α-Al matrix or plate-like Si particle, even with Yb addition up to 6100 ppm. The absence of Yb inside the eutectic Si particle may partly explain why no significant Si twinning was observed along {111}_Si planes in the eutectic Si particle. In addition, the formation of the thermodynamic stable YbP phases is also proposed to deteriorate the potency of AlP phase in Al alloys. This investigation highlights to distinguish the modification associated with the ever present P in Al alloys. We define modification as a transition from faceted to fibrous morphology, while a reduction of the Si size is termed refinement.     

Heterogeneous nucleation of solidification of Si by solid AI in hypoeutectic Al-Si alloy

Melt-spun Al-3 wt pct Si with and without ternary additions of Na and Sr has been heat-treated above the Al-Si eutectic temperature in a differential scanning calorimeter to form a microstructure of Al-Si eutectic liquid droplets embedded in the α-Al matrix. During subsequent cooling in the calorimeter, the heterogeneous nucleation temperature for solidification of Si in contact with the surrounding Al matrix depends sensitively on the alloy purity, with a nucleation undercooling which increases with increasing alloy purity from 9 to 63 K below the Al-Si eutectic temperature. These results are consistent with Southin’s hypothesis that low levels of trace P impurities are effective in catalyzing Si nucleation in contact with the surrounding Al matrix. With a low Al purity alloy, 0.1 wt pct Na addition increases the Si nucleation undercooling from 9 to 50 K, 0.15 wt pct Sr addition does not affect the Si nucleation temperature, and 0.3 wt pct Sr addition decreases the Si nucleation undercooling from 9 to 3 to 4 K. The solidified microstructure of the liquid Al-Si eutectic droplets embedded in the Al matrix depends on the Si nucleation undercooling. With low Si nucleation undercooling, each Al-Si eutectic liquid droplet solidifies to form one faceted Si particle; however, with high Si nucleation undercooling, each Al-Si eutectic droplet solidifies to form a large number of nonfaceted Si particles embedded in Al. Formerly with the Oxford Centre for Advanced Materials and Composites, Department of Materials, Oxford University     

Recycling of Magnesium Alloy Employing Refining and Solid Oxide Membrane (SOM) Electrolysis

Pure magnesium was recycled from partially oxidized 50.5 wt pct Mg-Al scrap alloy and AZ91 Mg alloy (9 wt pct Al, 1 wt pct Zn). Refining experiments were performed using a eutectic mixture of MgF₂-CaF₂ molten salt (flux). During the experiments, potentiodynamic scans were performed to determine the electrorefining potentials for magnesium dissolution and magnesium bubble nucleation in the flux. The measured electrorefining potential for magnesium bubble nucleation increased over time as the magnesium content inside the magnesium alloy decreased. Potentiostatic holds and electrochemical impedance spectroscopy were employed to measure the electronic and ionic resistances of the flux. The electronic resistivity of the flux varied inversely with the magnesium solubility. Up to 100 pct of the magnesium was refined from the Mg-Al scrap alloy by dissolving magnesium and its oxide into the flux followed by argon-assisted evaporation of dissolved magnesium and subsequently condensing the magnesium vapor. Solid oxide membrane electrolysis was also employed in the system to enable additional magnesium recovery from magnesium oxide in the partially oxidized Mg-Al scrap. In an experiment employing AZ91 Mg alloy, only the refining step was carried out. The calculated refining yield of magnesium from the AZ91 alloy was near 100 pct.     

X-Ray Videomicroscopy Studies of Eutectic Al-Si Solidification in Al-Si-Cu

Al-Si eutectic growth has been studied in-situ for the first time using X-ray video microscopy during directional solidification (DS) in unmodified and Sr-modified Al-Si-Cu alloys. In the unmodified alloys, Si is found to grow predominantly with needle-like tip morphologies, leading a highly irregular progressing eutectic interface with subsequent nucleation and growth of Al from the Si surfaces. In the Sr-modified alloys, the eutectic reaction is strongly suppressed, occurring with low nucleation frequency at undercoolings in the range 10 K to 18 K. In order to transport Cu rejected at the eutectic front back into the melt, the modified eutectic colonies attain meso-scale interface perturbations that eventually evolve into equiaxed composite-structure cells. The eutectic front also attains short-range microscale interface perturbations consistent with the characteristics of a fibrous Si growth. Evidence was found in support of Si nucleation occurring on potent particles suspended in the melt. Yet, both with Sr-modified and unmodified alloys, Si precipitation alone was not sufficient to facilitate the eutectic reaction, which apparently required additional undercooling for Al to form at the Si-particle interfaces.     

Cathodic reduction process of Al–Cu–Y alloy in fluoride-oxide eutectic system via molten salt electrolysis

Al-Cu-Y alloys were prepared by molten salt electrolysis in fluoride-oxide system composed of electrolyte(Na_3 AlF_6-AlF_3-LiF-MgF_2) and oxide(Al_2 O_3-CuO-Y_2 O_3). Cathodic reduction process of Al_2 O_3,CuO and Y_2 O_3 were analyzed by cyclic voltammetry and chronoamperometry. Components and phase composition of alloy samples prepared by potentiostatic electrolysis were characterized by scanning electron microscopy and energy dispersive spectroscopy. The results show that the Al-Cu-Y alloy can be prepared in the AIF_3-NaF-5 wt%LiF-5 wt%MgF2(NaF/AlF_3 = 2.2, molecular ratio) eutectic system with mixed oxide(Al_2 O_3-CuO-Y_2 O_3) through 2 h at the conditions of a temperature of 1208 K, cell voltage3.0 V, cathode current density 0.7 A/cm~2. Al(Ⅲ) and Cu(Ⅱ) ions can be reduced to zero valence Al(0) and Cu(0) directly on carbonaceous electrode surface by instantaneous nucleation, respectively, the reduction process is controlled by diffusion. The reduction potential of Y(Ⅲ) ions is close to the active ions of fluoride melts, but strengthened phase AI3 Y can be formed through electrochemical reduction and alloyed process with active Al(Ⅲ) and Cu(Ⅱ) ions, meanwhile, the Al_2 Cu and Al_3 Y phases are distributed at the grain boundary of Al matrix.     

Microstructure and High Temperature Impression Creep Properties of Mg–3Ca–xZr (x = 0.3, 0.6, 0.9 wt%) Alloys

The current study has investigated the influence of zirconium (Zr) addition to Mg–3Ca–xZr (x = 0.3, 0.6, 0.9 wt%) alloys prepared using argon arc melting on the microstructure and impression properties at 448–498 K under constant stress of 380 MPa. Microstructural analysis of as-cast Mg–3Ca–xZr alloys showed grain refinement with Zr addition. The observed grain refinement was attributed to the growth restriction effect of Zr in hypoperitectic Mg–3Ca–0.3 wt% Zr alloys. Heterogeneous nucleation of α-Mg in properitectic Zr during solidification resulted in grain refinement of hyperperitectic Mg–3Ca–0.6 wt% Zr and Mg–3Ca–0.9 wt% Zr alloys. The hardness of Mg–3Ca–xZr alloys increased as the amount of Zr increased due to grain refinement and solid solution strengthening of α-Mg by Zr. Creep resistance of Mg–3Ca–xZr alloys increased with the addition of Zr due to solid solution strengthening of α-Mg by Zr. The calculated activation energy (Q_a) for Mg–3Ca samples (131.49 kJ/mol) was the highest among all alloy compositions. The Q_a values for 0.3, 0.6 and 0.9 wt% Zr containing Mg–3Ca alloys were 107.22, 118.18 and 115.24 kJ/mol, respectively.     

Influence of treatment of melts by electromagnetic acoustic fields on the structure and properties of alloys of the Al–Si system

The influence of treating the melts by electromagnetic acoustic fields on the structure and properties of Al–12% Si and Al–20% Si binary alloys is investigated. In the course of experiments, the frequency of the electromagnetic field induced in the loop antenna varies as 500, 1000, and 2000 kHz. The melts are treated after their degassing and refining. It is established that this treatment method of the melts leads to a reduction of the total preparation time of alloy by 12% on average. The short-term treatment of the melts by electromagnetic acoustic fields promotes the refinement of the main phase components of alloys and an increase in their mechanical properties. When treating the Al–12% Si eutectic alloy with a frequency of 500 kHz, α-Al dendrites are refined from 30 to 22 μm and eutectic Si crystals are refined from 13 to 10 μm. When treating the Al–20%Si eutectic alloy with a frequency of 1000 kHz, eutectic Si crystals diminished from 8 to 5 μm and these of primary Si diminished from 90 to 62 μm. The ultimate tensile strength of the Al–12%Si eutectic alloy increases 13% under the mentioned treatment modes, while the relative elongation increases 17%; as for the Al–20% Si eutectic alloy, the same characteristics increases 9 and 65%, respectively. Based on these investigations, it is concluded that the selection of the treatment parameters of the melts of the Al–Si system by electromagnetic acoustic fields should be determined by the silicon content in the alloy. It is necessary to treat the melt by waves with a higher oscillation frequency with an increase in the silicon concentration. This treatment method makes it possible to form the modified fine-crystalline structure of alloy and, consequently, improves their mechanical properties. It can be successfully used when fabricating fine-crystalline foundry alloys and in the production of alloys of the Al–Si system. To determine the optimal treatment parameters depending on the structure of the initial charge and alloy nature, additional investigations are required.     

Investigation on the Effect of Sulfur and Titanium on the Microstructure of Lamellar Graphite Iron

The goal of this work was to identify the inclusions in lamellar graphite cast iron in an effort to explain the nucleation of the phases of interest. Four samples of approximately the same carbon equivalent but different levels of sulfur and titanium were studied. The Ti/S ratios were from 0.15 to 29.2 and the Mn/S ratios from 4.2 to 48.3. Light and electron microscopy were used to examine the unetched, color-etched, and deep-etched samples. It was confirmed that in irons with high sulfur content (0.12 wt pct) nucleation of type-A and type-D graphite occurs on Mn sulfides that have a core of complex Al, Ca, Mg oxide. An increased titanium level of 0.35 pct produced superfine interdendritic graphite (~10 μm) at low (0.012 wt pct) as well as at high-S contents. Ti also caused increased segregation in the microstructure of the analyzed irons and larger eutectic grains (cells). TiC did not appear to be a nucleation site for the primary austenite as it was found mostly at the periphery of the secondary arms of the austenite, in the last region to solidify. The effect of titanium in refining the graphite and increasing the austenite fraction can be explained through the widening of the liquidus-eutectic temperature interval (more time for austenite growth) and the decrease in the growth rate of the graphite because of Ti absorption on the graphite. The fact that Ti addition produced larger eutectic cells supports the theory that Ti is not producing finer graphite because of a change in the nucleation potential, but because of lower growth rate of the graphite in between the dendrite arms of a larger fraction of austenite. In the presence of high-Ti and S, (MnTi)S star-like and rib-like inclusions precipitate and act as nuclei for the austenite.     

Heterogeneous nucleation of solidification of Si in Al-Si and Al-Si-P alloys

Heterogeneous nucleation of solidification in melt spun Al-Si and Al-Si-P has been studied using differential scanning calorimetry, and transmission, scanning transmission and high resolution electron microscopies. The microstructures of the heat treated melt spun alloys all consist of an Al matrix, Al-Si eutectic distributed along the Al grain boundaries, and Si embedded in the Al matrix. The Si microstructure depends on the level of P: coarse faceted Si particles are nucleated by AlP particles in Al-Si containing 2 ppm P and Al-Si-P containing 35 ppm P whereas eutectic droplets of fine Si particles are nucleated by the surrounding Al matrix at a high undercooling in Al-Si containing 0.25 ppm P. The Si nucleation onset temperature remains approximately constant while the peak and end temperatures both decrease with increasing cooling rate, in agreement with classical nucleation theory. Kinetic analysis, using the spherical cap model gives contact angles of 10°, 43° and 10° for Si nucleation in low and high purity Al-Si and Al-Si-P respectively.     

Eutectic Morphology of Al-7Si-0.3Mg Alloys with Scandium Additions

The mechanisms of Al-Si eutectic refinement due to scandium (Sc) additions have been studied in an Al-7Si-0.3Mg foundry alloy. The evolution of eutectic microstructure is studied by thermal analysis and interrupted solidification, and the distribution of Sc is studied by synchrotron micro-XRF mapping. Sc is shown to cause significant refinement of the eutectic silicon. The results show that Sc additions strongly suppress the nucleation of eutectic silicon due to the formation of ScP instead of AlP. Sc additions change the macroscopic eutectic growth mode to the propagation of a defined eutectic front from the mold walls opposite to the heat flux direction similar to past work with Na, Ca, and Y additions. It is found that Sc segregates to the eutectic aluminum and AlSi₂Sc₂ phases and not to eutectic silicon, suggesting that impurity-induced twinning does not operate. The results suggest that Sc refinement is mostly caused by the significantly reduced silicon nucleation frequency and the resulting increase in mean interface growth rate.     

Consolidation of Carbon Nanotube Reinforced Aluminum Matrix Composites by High-Pressure Torsion

Al-3 vol pct carbon nanotube (CNT) composites are fabricated by consolidation through high-pressure torsion (HPT) at room temperature. The densification behavior, microstructural evolution, and mechanical properties of Al/CNT composites are studied. The results show that density and microstructural homogeneity increase with increasing number of revolutions under a high pressure of 6 GPa. Substantial grain refinement is achieved after 10 turns of HPT with an average grain thickness of ~38 nm perpendicular to the compression axis of HPT. The Al/CNT composite shows a considerable increase in hardness and strength compared to the Al matrix. The strengthening mechanisms of the Al/CNT composite are found to be (i) grain refinement of Al matrix and (ii) Orowan looping. Raman spectroscopy and high-resolution transmission electron microscopy reveal that the structure of most of CNTs is changed during processing through mechanical milling and HPT.     

Heterogeneous nucleation of Al2Cu in AlCu eutectic liquid droplets embedded in an al matrix

The heterogeneous nucleation of Al₂Cu in AlAl₂ Cu eutectic liquids droplets embedded in an Al matrix has been studied by a combination of optical microscopy, transmission electron microscopy and differential scanning calorimetry. Nucleation of Al₂Cu is stimulated catalytically by the surrounding matrix at a temperature approx. 25°C below the eutectic temperature. With increasing cooling rate, the solidification onset, peak and end temperatures decrease and the peak height and width of the solidification exotherm increase. the contact angle at the AlAl₂ Cu liquid triple point is calculated to be 24.6° from the variation of exothermic peak width with cooling rate, but the corresponding calculated value of the number of potential catalytic nucleation sites is physically unrealistic.