Microstructure evolution and phase transformation of traditional cast and spray-formed hypereutectic aluminium-silicon alloys induced by heat treatment

Microstructural evolution and phase transformation induced by different heat treatments of the hypereutectic aluminium-silicon alloy, Al-25Si-5Fe-3Cu （wt%, signed as 3C）, fabricated by traditional cast （TC） and spray forming （SF） processes, were investigated by differential scanning calorimetry （DSC） and scanning electron microscopy （SEM） combined with energy dispersive X-ray spectroscopy and X-ray diffraction techniques. The results show that A17Cu2Fe phase can be formed and transformed in TC- and SF-3C alloys between 802-813 K and 800-815 K, respectively. The transformation from β-Al5FeSi to δ-Al4FeSi2 phase via peritectic reaction can occur at around 858-870 K and 876-890 K in TC- and SF-3C alloys, respectively. The starting precipitation temperature of δ-Al4FeSi2 phase as the dominant Fe-bearing phase in the TC-3C alloy is 997 K and the exothermic peak about the peritectic transformation of δ-Al4FeSi2→β-Al5FeSi is not detected in the present DSC experiments. Also, the mechanisms of the microstructural evolution and phase transformation are discussed.

Functions and mechanism of modification elements in eutectic solidification of Al-Si alloys:A brief review

Being used more and more widely in engineering,AlSi alloys comprise about 80%of all kinds of aluminum alloys,which are the most widely utilized nonferrous alloys.Although most Al-Si alloys consist of multiple components,the eutectics in the structure accounts for 50%-90%of the sum volume of such alloys.Therefore,understanding the modification mechanism and function rules of the AlSi eutectic solidification is the technical key in controlling the structures and properties of such casting alloys.The present paper chiefly reviews recent investigation developments and important conclusions along the lines of the functions of modification elements and their modification mechanism in the eutectic solidification of Al-Si alloys.

Solidification structure of eutectic Al-Si alloy under a high magnetic field-aid-electromagnetic vibration

An electromagnetic vibration was generated by simultaneously imposing a strong static magnetic field （up to 10 T） and an alternative electricity current to the metal. Its effects on the solidification structure of eutectic Al-Si alloy have been investigated experimentally. It is found that the eutectic structure has been refined by solely imposing high magnetic field while it is coarsened under the electromagnetic vibration. Furthermore, polyhedral Si grains and non-dendritic α-Al appeared when the electromagnetic vibration strength was strong enough. The refining of eutectic structure is attributed to the decrease of diffusion coefficient caused by the strong magnetic field. The coarseness of eutectic structure may be attributed to the convection caused by electromagnetic vibration. Strong convection may break co-operative growth of eutectic phases to form polyhedral Si grains and non-dendritic α-Al.

Distributions of Sr and Fe and their influence on modification of hypoeutectic Al-Si alloy

The influence of cooling rate and Fe-containing phases on Sr-modification of Si phases in hypoeutectic Al-Si alloys, a problem with great industrial importance, was investigated. The microstructures of samples were examined using scanning electron microscopy(SEM) with energy-dispersive X-ray spectroscopy(EDX). A new method of electron probe microanalysis(EPMA) map scanning was used to analyze the Sr distribution, which gave quantitative results covering more Si particles. EPMA map scanning, together with SEM with EDX, was also used in analyzing the distribution of Fe phases. Results show that Fe-containing phase was related to the unmodified Si particles in samples with partial modification failure and the plate-like Si phases in samples without modification failure. Such a relationship was further confirmed by the microstructure observation.In conclusion, a partial failure of Sr-modification can be caused by both slow cooling rate and Fe-containing phases.

Electromagnetic Filtration of Primary Fe-Rich Phases from Al-Si Alloy Melt

Electromagnetic filtration of primary Fe-rich phases (complex compound of AlFeSiMn) from Al-Si alloy melt containing 1.2 wt pct Fe have been studied by theoretical analysis and on a self-designed electromagnetic filtration equipment. The principle of the electromagnetic filtration is that the EMF (electromagnetic force) scarcely acts on the primary Fe-rich phases having low electric conductivity, which are then moved in the direction opposite to that of the EMF. Experimental results show that the primary Fe-rich phases are separated from Al-Si alloy melt and are collected in the filter while the melt is in horizontal flow. The removal efficiency of the primary iron-phases (77) calculated is less as the greatest flow velocity of the melt (UM) and the height of the filter (2h) are larger, while it becomes larger as EMF, operating distance of electromagnetic force (cr) and particle size (dv) become larger. It has been confirmed that the primary iron-phases larger than 20 jim can be removed efficiently by theoretical analysis and experiments. This new technique is high efficient and available for continuously flowing melts as compared with natural settling and filtration methods, which offer a possibility for recycling high quality aluminum alloys.

Phase-field simulation of lamellar growth for a binary eutectic alloy

Using general multi-phase-field model,detailed microstructures corresponding to different initial lamellar sets were simulated in a binary eutectic alloy with an asymmetric phase diagram.The simulation results show that regular or unstable oscillating lamellar structures depend on the initial lamellar widths of two solid phases.A lamellar morphology map associating with the initial widths has been derived,which is capable of showing the condition of forming various lamella structures.For instance,a regular lamella was formed with fast solidification while large lamella resulted from disorder growth with low interfacial velocity. The investigated interface velocities indicate that with fast solidification to form regular lamella,a disorder growth manner or a large lamellar spacing causes a low interface velocity.These results are in good agreement with those proposed by Jackson-Hunt model.

The Collins Model and the Eutectic—Type and the Peritectic—Type Phase Diagrams

From the Gibbs free energy and the equations of two-phase equilibrium curves of the two-dimensionalbinary system which has the Lennard-Jones potential, using the Collins model, the eutectic-type phase diagram and theperitectic-type phase diagram of the binary system are obtained, whose results are quite similar to the behavior of thethree-dimensional (3D) substances.

Effect of eutectic phase on damping and mechanical properties of as-cast Mg-Ni hypoeutectic alloys

Dynamic mechanical analysis (DMA) was applied to systematically investigate the low frequency damping properties of as-cast hypoeutectic Mg-Ni alloys. The results show that the as-cast hypoeutectic Mg-Ni alloys exhibit high damping capacities. The strain amplitude dependent damping curve has its own special characteristic, in which the damping is strongly related to the strain amplitude. The effect of the eutectic phase on damping and the mechanical properties of as-cast hypoeutectic Mg-Ni alloys were also discussed in detail.

NONSTABLE GROWTH OF Al-Si EUTECTIC IN CONSTRAINED CONDITION

Nonstable growth of Al-Si eutectic in constrained condition has been investigated by means of change of the withdrawing rate in an unidirectional solidification system,In constant acceleration growth,a retarded effect of response of eutectic interflake spacing on the growth rate has been observed.The response mechanisms are cluster-branching and local termination extension of Si-phase.In constant deceleration growth,the cluster-branching and termina- tion mechanisms of silicon still control adjustment of the interflake spacing,but the spacing is determined by the initial growth rate and does not respond to the decreasing growth rate.

Experimental Study and Thermodynamical Calculation on the Formation of Eutectic Phase of MnS-RE_2S_3 and(Mn,Ca)S-RE_2S_3 in Sulfur-Containing Free-Cutting Steel

The free-cutting phase in RE or Ca-RE treated sulfur-containing free-cutting steel is the eutectic phases of MnS-RE_2S_3 and (Mn,Ca)S-RE_2S_3,respectively.The atomic ratio of RE/S needed to modify all the MnS into the eutectic phase is higher than 1.48 or 1.41-1.37 Ca/S,when RE or Ca-RE is used as the modifiz- er in the sulfur-containing free-cutting steel.Moreover,the thermodynamical calculation shows that the eutectic temperature is lower than the solidifying temperature,which is the key condition for the eutectic phase to keep globual during solidifying.

RELATIONSHIP BETWEEN METASTABLE EXTENSION OF SOLID SOLUBITY OF EUTECTIC SYSTEMS AND PHASE DIAGRAM

A criterion of the metastable extension of solid solubility was proposed.When the eutectic concentration arm ratio parameter of an alloy,J>10,the hypereutectic extension and the metastable solid solubility limit beyond eutectic concentration may be obtained.When J≤10, the hypoeutectic extension may be obtained.The extension parameter,C_(eq)~s/C_(cu),is directly proportional to the parameter J.Thus,it seems easy to predict the tendency of the solid solu- hility extension under rapid solidification on the basis of the eutectic phase diagram.

Preparation and Characterization of CA-MA Eutectic/Silicon Dioxide Nanoscale Composite Phase Change Material from Water Glass via Sol-Gel Method

This work mainly involved the preparation of a nano-scale form-stable phase change material（PCM） consisting of capric and myristic acid（CA-MA） binary eutectic acting as thermal absorbing material and nano silicon dioxide（nano-SiO_2） serving as the supporting material. Industrial water glass for preparation of the nano silicon dioxide matrix and CA-MA eutectic mixture were compounded by single-step sol-gel method with the silane coupling agent. The morphology, chemical characterization and form stability property of the composite PCM were investigated by transmission electron microscopy（TEM）, scanning electron microscopy（SEM）, Fourier-transform infrared（FT-IR） spectroscopy and polarizing microscopy（POM）. It was indicated that the average diameter of the composite PCM particle ranged from 30-100 nm. The CA-MA eutectic was immobilized in the network pores constructed by the Si-O bonds so that the composite PCM was allowed no liquid leakage above the melting temperature of the CA-MA eutectic. Differential scanning calorimetry（DSC） and thermogravimetric analysis（TGA） measurement were conducted to investigate the thermal properties and stability of the composite PCM. From the measurement results, the mass fraction of the CA-MA eutectic in the composite PCM was about 40%. The phase change temperature and latent heat of the composite were determined to be 21.15 ℃ and 55.67 J/g, respectively. Meanwhile, thermal conductivity of the composite was measured to be 0.208 W·m^（-1）·K^（-1） by using the transient hot-wire method. The composite PCM was able to maintain the surrounding temperature close to its phase change temperature and behaved well in thermalregulated performance which was verified by the heat storage-release experiment. This kind of form-stable PCM was supposed to complete thermal insulation even temperature regulation by the dual effect of relatively low thermal conductivity and phase change thermal storage-release properties. So it can be formulated that the nanoscale CA-MA/SiO_2 composite PCM with the form-stable property, good thermal storage capacity and relatively low thermal conductivity can be applied for energy conservation as a kind of thermal functional material.

Phase selection in highly undercooled Fe-B eutectic alloy melts

The high undercooling technique by molten glass slag purification and cyclical superheating in Ar atmosphere was applied to bulk Fe-B alloy melts. A hypercooling was achieved which suppressed the formation of stable phase and consequently promoted the nucleation of metastable phase. Fe-17%B and Fe-20%B alloys were investigated, respectively. TEM and X-ray powder diffraction analyses verify the formation of metastable phase in the highly undercooled Fe-B alloy melts. Besides, the critical nucleation work of Fe2B and Fe3B phases was calculated to predict phase selection in the undercooled melts. The results show that the metastable phase formation is a function of the undercooling achieved prior to nucleation. And the amount of undercooling is an important factor in determining microstructural development by controlling phase selection in the undercooled melts.

Effects of individual and combined additions of phosphorus,boron and cerium on primary and eutectic silicon in an Al-30Si alloy

The modification of silicon in an Al-30Si alloy was studied using optical microscopy, electron probe micro-analysis, transmission electron microscopy and differential scanning calorimetry. It is found that phosphorus master alloys combined with boron master alloys have good modification effect on primary silicon but no evident modification effect on eutectic silicon, while boron combined with cerium has good modification effect on eutectic silicon. The results of differential scanning calorimetry show that phosphorus, boron or cerium addition and their combined addition have different undercooling effects on eutectic silicon. Many scholars thought that AlP particles were the nuclei of eutectic silicon when phosphorus was enough in the alloy. Our results show that β-（Al,Si,Fe） can still be the nucleus of plate-like entectic silicon while AlP is the nucleus of primary silicon when there is enough phosphorus in the melt. In addition, the mechanism about the modification was also discussed.

Modeling of aluminum-silicon irregular eutectic growth by cellular automaton model

Due to the extensive application of Al-Si alloys in the automotive and aerospace industries as structural components, an understanding of their microstructural formation, such as dendrite and(Al+Si) eutectic, is of great importance to control the desirable microstructure, so as to modify the performance of castings. Since previous major themes of microstructural simulation are dendrite and regular eutectic growth, few efforts have been paid to simulate the irregular eutectic growth. Therefore, a multiphase cellular automaton(CA) model is developed and applied to simulate the time-dependent Al-Si irregular eutectic growth. Prior to model establishment, related experiments were carried out to investigate the influence of cooling rate and Sr modification on the growth of eutectic Si. This CA model incorporates several aspects, including growth algorithms and nucleation criterion, to achieve the competitive and cooperative growth mechanism for nonfaceted-faceted Al-Si irregular eutectic. The growth kinetics considers thermal undercooling, constitutional undercooling, and curvature undercooling, as well as the anisotropic characteristic of eutectic Si growth. The capturing rule takes into account the effects of modification on the silicon growth behaviors.The simulated results indicate that for unmodified alloy, the higher eutectic undercooling results in the higher eutectic growth velocity, and a more refined eutectic microstructure as well as narrower eutectic lamellar spacing. For modified alloy, the eutectic silicon tends to be obvious fibrous morphology and the morphology of eutectic Si is determined by both chemical modifier and cooling rate. The predicted microstructure of Al-7Si alloy under different solidification conditions shows that this proposed model can successfully reproduce both dendrite and eutectic microstructures.

Evolution of eutectic structures in Al-Zn-Mg-Cu alloys during heat treatment

The evolution of the eutectic structures in the alloys with different copper contents during heat treatment was studied by scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), and differential scanning calorimetry(DSC). The as cast microstructures involve α(Al), eutectic(α(Al) + Mg(Al, Cu, Zn)2) and Al7Cu2Fe. The Al2CuMg particles form during heat treatment. The volume of coarse phases decreases quickly in the initial 12 h during heat treatment. The volume of coarse phases change a little at 400 and 420 ℃. Copper content has a great influence on the evolution of the eutectic. The coarse phases dissolve slowly in alloy with higher copper content.

Thermal Energy Storage Characteristics of Myristic and Stearic Acids Eutectic Mixture for Low Temperature Heating Applications

Stearic acid (67.83℃) and myristic acid (52.32℃) have high melting temperatures that can limit their use as phase change material (PCM) in low temperature solar heating applications such as solar space and greenhouse heating in regard to climatic requirements. However, their melting temperatures can be adjusted to a suitable value by preparing a eutectic mixture of the myristic acid (MA) and the stearic acid (SA). In the present study, the thermal analysis based on differential scanning calorimetry (DSC) technique shows that the mixture of myristic acid (MA) and stearic acid (SA) in the respective composition (by mass) of 64% and 36% forms a eutectic mixture having melting temperature of 44.13℃ and the latent heat of fusion of 182.4J·g-1. The thermal energy storage characteristics of the MA-SA eutectic mixture filled in the annulus of two concentric pipes were also experimentally established. The heat recovery rate and heat charging/discharging fractions were determined with respect to the change in the mass flow rate and the inlet temperature of heat transfer fluid. Based on the results obtained by DSC analysis and by the heat charg- ing/discharging processes of the PCM, it can be concluded that the MA-SA eutectic mixture is a potential material for low temperature thermal energy storage applications in terms of its thermo-physical and thermal characteristics.

An Al-12Si/ZnS powder inoculant for eutectic silicon in Al-12Si alloy

To obtain high-performance Al-Si-based cast alloys,refinement and modification of Si phases are required.An Al-12Si/ZnS powder inoculant was designed and fabricated using a chemical bath deposition method.The efficiency of the inoculant for modifying the eutectic Si phase in as-cast Al-12Si alloy was studied.Results show that Al-12Si/ZnS powder can significantly refine the eutectic Si in Al-Si cast alloys.The best refinement effect for eutectic Si is achieved with 17.5wt.%Al-12Si/ZnS powder.Coarse long needle-shaped eutectic Si with a length of 18μm was modified into approximately spherical shape with a diameter of 6.53μm,which is evenly distributed throughout the alloy.The E2EM model calculation indicates that the inter-plane misfit(F_(p))and inter-atomic spacing misfit(F_(r))between ZnS and Si are all less than 0.5%,which confirms that ZnS is a potential nucleation site for Si phase.The hardness,tensile strength,and elongation of Al-12Si alloys modified with 17.5%Al-12Si/ZnS powder increase 6.30%,16.18%and 55.45%,respectively,compared to the unmodified Al-12Si alloy.The fracture behavior of the alloy with 17.5wt.%Al-12Si/ZnS powder is dominated by transgranular fracture supplemented by intergranular fracture.

SCALING LAW OF IRREGULAR EUTECTIC IN DIRECTIONAL SOLIDIFICATION

The profile features of the solidifying interface of the irregular Al-Si eutectic during directional solidification are studied by numerically solving a nonlinear coupling equation of directional solidification of this eutectic.The critical splitting point of the solidifying interface coincides with the maximum value of its position and corresponds to the marginal stability point.Argument is presented that the interlamellar spacing for local regular structure selects the critical splitting state of the α(Al)-liquid interface as its operating point,and the oper- ating point of the average interflake spacing for the irregular structure is the critical splitting state of the β(Si)-liquid interface.The scaling laws derived,which have the more general forms than the classic Jackson-Hunt scaling,gained support from the experimental results.

Si-RICH LAYER FORMATION DURING DIRECTIONAL SOLIDIFICATION OF AI-Si EUTECTIC ALLOY IN ELECTROMAGNETIC FIELD

The formation of a special Si-rich layer on the periphery of Al-Si eutectic alloy specimen during directional solidification in rotary electromagnetic field has been investigated.This layer seems due to the migration of some Si grains onto the crucible wall,then stagnating and coarsening further.