Thermodynamic Criteria for the Selection of Alloys Suitable for Semi‐Solid Processing

In this work the suitability of alloys for semi‐solid processing was investigated using numeric simulation. The simulation was based on equilibrium calculations, Scheil‐Gulliver calculations and, when necessary, diffusion simulations. For this purpose a new parameter was introduced in addition to the commonly used selection criteria. With the new parameter, the thixo ranges ΔT^40–60 and ΔT^20–40, the specific demands of the different semi‐solid processes thixocasting and thixoforging can be considered. On the basis of thermodynamic simulation, the conventional aluminium alloys A356, AA6082 and A319, the steels 100Cr6, HS6‐5‐2 and X210CrW12 and a number of experimental aluminium‐lithium based alloys were evaluated according to the selection criteria. The thermodynamic calculations showed a large sensitivity of the course of the solidification with respect to variations in the contents of the alloying elements. This shows the necessity of keeping a tight composition control on alloys for semi‐solid processing. For aluminium alloys in particular silicon has to be monitored closely and for steels carbon and chromium.     

On differential thermal analyzer curves for the melting and freezing of alloys

Using a heat-flow model of a differential thermal analyzer and thermal characteristics obtained by fitting experimental results for a pure metal, the response of the differential thermal analyzer is modeled for the melting and solidification of alloys. The enthalpy-temperature relation used for the alloy simulations is obtained by two different methods: (1) equilibrium and Scheil considerations derived solely from thermodynamic information and (2) solute-diffusion micromodels coupled to the differential thermal analysis (DTA) heat-flow equations. During the consideration of pure material melting, simple expressions are obtained for the effect of sample size and heating rate on the DTA melting onset temperature, peak temperature, and peak height, which assist in the proper calibration of a differential thermal analyzer. For alloys, the smearing effect of the DTA heat flow at different heating and cooling rates is demonstrated for various solidification-path features. In particular, the DTA peak temperature during melting, which is often selected as the liquidus temperature experimentally, is shown to be significantly higher than the liquidus temperature for small-freezing-range alloys and/or for alloys with slow solid diffusion. The DTA curves calculated for freezing with dendritic growth due to supercooling, quantify the errors associated with the determination of the liquidus temperature on cooling.     

Computer simulation of the brittle‐temperature‐range (BTR) for hot cracking in steels

The hot‐cracking susceptibility of a material is usually evaluated by means of a characteristic temperature range, the so‐called brittle‐temperature‐range (BTR). The upper bound of the BTR is determined by the zero‐strength‐temperature (ZST), the lower limit is defined by the zero‐ductility‐temperature (ZDT). In the present work both ZDT and ZST are related to the current amount of residual liquid during solidification, which in turn is evaluated from a modified Scheil‐Gulliver micro‐segregation model, which takes into account back diffusion of interstitial alloying components. This model is particularly suitable for application to high‐order alloy systems. The calculated values of the ZDT are compared to numerous experimental results from literature and good agreement is achieved. It is demonstrated that the application of the classical Scheil‐Gulliver model does not give feasible results.     

Hot-tearing susceptibility of Al–Zn alloys

The modern concepts of the causes of hot tearing are considered and the influence of the solid fraction growth rate of an alloy is studied. The hot-tearing susceptibility (HTS) of binary Al–(5–73) wt % Zn alloys is investigated using backbone tests. The HTS is found to be maximal at ~25 wt % Zn. This maximum cannot be explained by a change in the effective solidification range, since this range of the alloys decreases monotonically with increasing zinc content. The calculations of nonequilibrium solidification by the Scheil–Gulliver model and the solid fraction growth rate of the alloys under study demonstrate that the increase in the HTS induced by an increase in the zinc content from 5 to 25 wt % is related to the decrease in the solid fraction growth rate at the final stages of solidification. The decrease in the HTS at >25 wt % Zn is associated with an increase in the fraction of eutectic in the alloys (the solid fraction growth rate during the eutectic reaction tends toward infinity) and with a change in its morphology.     

DTA‐Measurements to Determine the Thixoformability of Steels

Semi‐solid metallurgy (SSM), also known as “thixoforming” or “thixoprocessing”, is of special interest as a new potential manufacturing technology for components in the automobile, machine and electronic industries. The aim of this technology is to produce complex shapes which cannot be produced with conventional processing methods. An important process step of semi‐solid processing (SSP) is the reheating and isothermal holding of the billet within the solid‐liquid range in order to obtain the required fraction liquid content and the desired globular microstructure. Aside from the investigation of billet heating and the development of a suitable tool design, the development and evaluation of adequate microstructures over a wide temperature area is very important. The focus of this paper is to determine the semi‐solid area of different steels through Differential Thermal Analysis (DTA) measurements. To determine a process window for handling the alloys in the semi‐solid state, the DTA‐results can be combined with microstructure parameters. Subsequent quenching experiments show the development of the microstructure parameters (e.g. grain size, phase distribution, volume fraction, shape factor, matrix character, contiguity, and particle density of the primary solid and liquid phases). A comparison of the slopes of the determined solid‐liquid areas for different steels show the width of the melting or freezing intervals to evaluate the possible process windows. DTA‐experiments performed at different heating rates show the influence of faster heating and cooling rates on the solidus‐liquidus interval. To evaluate the suitability for the thixoforming processes, this paper describes, and then compares, the semi‐solid intervals of different steel grades, which have been investigated in the Department of Ferrous Metallurgy at the RWTH Aachen University. The tool steel HS 6‐5‐3 and the cold work tool steel X210CrW12 have a wide semi‐solid area, which can be explained due to the dissolution of different carbides. In contrast to this, the steels C45, 42CrMo4, 16MnCr5, 34CrNiMo4, 100Cr6, X220CrVMo13‐4 and the Alloy 33 show a much smaller semi‐solid area.     

New Composition Based Technique for Solidification Cracking Resistance Evaluation

Predicting the occurrence of solidification cracking during the solidification of metallic alloys by numerical simulation is a crucial move for avoiding such defects. Several models are widely available, however, the application of such are impacted due to the specific and not accessible parameters required. A simple, composition-based approach to rank solidification cracking susceptibility is presented. The procedure links computational thermodynamic and computational fluid dynamics (CFD) to provide an evaluation tool for solidification cracking. The method is related to the liquid filling phenomena in dendritic arms during solidification, which plays a critical role in solidification cracking phenomena. The dendritic profiles were constructed using the fraction of solid calculated by commercial thermodynamic software packages. The calculated results were compared with experimental solidification cracking data and showed satisfactory accuracy. The method capability to rank the solidification cracking propensity of similar alloys based on composition provides an important new operative tool to aid alloy development in welding and additive manufacturing related areas.

     

先进高强韧Al-Zn-Mg-Cu合金凝固和均匀化组织及相构成

采用热力学计算与实验相结合的方法,研究了两种高强韧Al-Zn-Mg-Cu合金铸态及均匀化态的显微组织和相构成.铸态A合金主要由Mg（Zn,Al,Cu）₂相和少量Al₂Cu相组成,而铸态B合金仅含Mg（Zn,Al,Cu）₂相.热力学计算显示,A和B两种合金的实际凝固过程介于Lever Rule和Scheil Model两种模拟结果之间,由于合金成分不同而导致的铸态A和B合金中各相含量差异与Scheil Model模拟所得到的各相摩尔分数变化规律基本一致.经常规工业均匀化处理（460℃保温24 h）,铸态A和B合金中存在的Mg（Zn,Al,Cu）₂或Al₂Cu相均能充分回溶,并得到单相α（Al）基体,这与热力学计算所得到的AlZn-Mg-Cu四元系统在7.5%Zn条件下460℃等温相图相符合.      

Microstructural investigations in the semi‐solid state of the steel X210CrW12

Thixoforming is an emerging young technology to produce complex structural parts and near net shape components. Thixoforming stands for the forming of materials in the semi‐solid state. One precondition for the thixoformability of materials is the minimum temperature range for the solidus‐liquidus interval and the globulitic formation of the solid phase during the thixoforming process. Besides this other parameters like shape factor, contiguity, matrix character, melting interval, and phase distribution are important process parameters. Aluminium and magnesium alloys are the objectives of numerous investigations, but research activities concerning the thixoformability of steel alloys have been commenced recently. This article provides metallographic information on the relevant parameters of the steel X210CrW12, taking into account the microstructural evolution and the establishment of a parameter field for forming this material in the semi‐solid state.     

Semi‐Solid Rheoforging of Steel

To produce steel components with complex shapes excessive machining is necessary frequently since high pressure die casting of steel is not industrially applied. Forming steel in the semi‐solid state can in principle produce new components and geometries which cannot be realised by conventional closed die forging. Semi‐solid forging of steel combines the possibility of producing geometries not conventionally forgeable in one forming operation and of adding further functions during the same operation. In previous investigations on thixoforming of steels, the semi‐solid steel was generated by reheating precursor material billets. An alternative approach for generating semi‐solid steel from the liquid state with subsequent forging operation is presented in this paper for the first time. The steel grades X210CrW12 cold work tool steel and 100Cr6 bearing steel are molten and driven into a globular semi‐solid state using a cooling slope and a cup. By cooling the steel into the semi‐solid range instead of heating it, the required process temperatures are lower than in the process route via heating. Therefore, the load on the dies in a semi‐solid forging operation is decreased. Suggestions for the respective layout of the process are made for both steel grades. Future potentials and challenges to be solved are discussed, showing advantages especially in the field of high melting point alloys such as steels. This technique enables to produce pre‐shaped semi‐solid billets to optimise the materials flow and the homogeneity of the mechanical properties.     

Effect of composition on the solidification behavior of several Ni-Cr-Mo and Fe-Ni-Cr-Mo alloys

The microstructural development of several Ni-Cr-Mo and Fe-Ni-Cr-Mo alloys over a range of conditions has been examined. A commercial alloy, AL-6XN, was chosen for analysis along with three experimental compositions to isolate the contribution of individual alloying elements to the overall microstructural development. Detailed microstructural characterization on each alloy demonstrated that the observed solidification reaction sequences were primarily dependent on the segregation behavior of molybdenum (Mo), which was unaffected by the large difference in cooling rate between differential thermal analysis (DTA) samples and welded specimens. This explains the invariance of the amount of eutectic constituent observed in the microstructure in the welded and DTA conditions. Multicomponent liquidus projections developed using the CALPHAD approach were combined with solidification path calculations as a first step to understanding the observed solidification reaction sequences. Discrepancies between the calculations and observed reaction sequences were resolved by proposing slight modifications to the calculated multicomponent liquidus projections.     

Sensitivity of Thermophysical Material Properties on Solidification Simulation of Al-Si Binary Alloys

The challenges in the numerical simulation of the solidification of binary alloys are not only in the complexity of the algorithms themselves, but also in the validity of the data used to define the material properties of the various phases to obtain a valid simulation. The effect of material properties on the numerical simulations was investigated in the present study wherein the Al-3 wt pct Si hypoeutectic binary alloy was solidified such that the solidification front traveled against the gravity vector (upward solidification). Numerical simulations were carried out with a new algorithm that was developed to include the effect of undercooling of the liquid temperature prior to the solidification event. The effect of specific heat of solid, density of solid, solute diffusivity coefficient of liquid, and thermal conductivity of solid on transient temperature distribution and solidification start time at mushy zone/liquid interface was investigated. It was found that specific heat and thermal conductivity of the solid could not be assumed as constants, whereas most properties in the liquid phase could be assumed as constants for the temperature range used in the study and the experiments used for validation (low initial melt superheat temperature). These properties were enumerated and quantified. The results of the numerical simulations using the optimum set of material properties were validated by experiments.     

Semi‐Solid Processing of Metal Alloys

Semi‐solid metal casting is an innovative technology for the production of near‐net‐shape parts with demanding mechanical properties. The paper describes different processing routes and materials for semi‐solid‐metal casting (SSM), which have been investigated and also partially developed at the Foundry‐Institute of Aachen University. The standard thixocasting process for aluminium, highly reactive magnesium alloys and steel alloys with high melting points was investigated under variation of a wide range of process parameters. Specially adapted pre‐material production and reheating methods were developed for different materials and their application and future potential is pointed out. The thixocasting experiments were executed on a modified high pressure die‐casting machine with a specially designed “step‐die” providing wall thicknesses from 0.5 to 25 mm. The mechanical properties were tested in dependence of the wall thickness and the metal velocity. The results of these examination show high tensile strength values in combination with very good elongations. The rheocasting process is a new SSM‐forming method with liquid melt as feed‐stock and a high recycling potential. The research results of RCP‐technology (Rheo‐Container‐Process) invented at the Foundry‐Institute and of the Cooling‐Channel‐Process for aluminium and magnesium alloys are promising and are presented in this paper. Studies on semi‐solid processing of magnesium alloys and mixtures of them were conducted by Thixomolding^TM. To establish the most adequate process parameters, the temperature and the mixture relations were varied. Using a mould for tensile test specimens, the mechanical properties and the microstructure evolution could be evaluated. The chemical composition of the different phases was determined using SEM and EDX technologies. Evaluations of the flowing properties were conducted using a spiral mould with a total length of 2m and a cross section of 20mm x 1.5mm.     

Modeling solidification of turbine blades using theoretical phase relationships

The solidification of hot-stage turbine blades made from René N4 nickel-base superalloy has been modeled to show the morphology of porosity and the local changes in solute concentration. The key task of the present study was the calculation of the solid-liquid phase equilibria of this 9-component nickel-base superalloy from the thermodynamic values of these phases. The Gibbs energies of the solid and liquid phases were obtained from those of the 36 binaries using the Muggianu and Kohler methods of extrapolation. The phase equilibrium data were then used to compute the change in fraction solid with temperature, initially using the complete mixing approximation (Scheil equation). The predicted freezing range was somewhat longer than measured. A modified Scheil equation was derived assuming incomplete mixing. Assuming 60 pct mixing of the solute, the calculated freezing range agreed with experiments. Fraction solid temperature allowed the detailed morphology of the“mushy”zone to be predicted. Using measured dendrite spacings and assuming the crystals to grow in a cubic array, the shape of the crystals and, consequently, the size of the liquid channels were predicted as a function of position. Hence, computation of the rate of fluid flow in the channels (from the known changes of temperature with time) allowed the pore morphology to be inferred.     

Development of Mn-Cr-(C-N) Corrosion Resistant Twinning Induced Plasticity Steels: Thermodynamic and Diffusion Calculations,Production, and Characterization

In this work, the development of corrosion-resistant twinning induced plasticity steels is presented, supported by thermodynamic and diffusion calculations within the (Fe-Mn-Cr)-(C-N) alloy system. For the calculations, ambient pressure and primary austenitic solidification were considered as necessary to avoid nitrogen degassing in all processing steps. Manganese is used as an austenite stabilizer, chromium is used to increase nitrogen solubility and provide corrosion resistance, and carbon and nitrogen are used as interstitial elements to provide mechanical strength. Isopleths of the different elements vs temperature as well as isothermal sections were calculated to determine the proper amount of Mn, Cr, total interstitial content, and the C/N ratio. Scheil and diffusion calculations were used to predict the extent of microsegregations and additionally to evaluate the effect of diffusion annealing treatments. The materials were produced in laboratory scale, being followed by thermomechanical processing and the characterization of the microstructure. Tensile tests were performed with three different alloys, exhibiting yield strengths of 460 Mpa to 480 MPa and elongations to fracture between 85 pct and 100 pct.     

Solidification and Microstructural Evolution of Hypereutectic Al-15Si-4Cu-Mg Alloys with High Magnesium Contents

The low coefficient of thermal expansion and good wear resistance of hypereutectic Al-Si-Mg alloys with high Mg contents, together with the increasing demand for lightweight materials in engine applications have generated an increasing interest in these materials in the automotive industry. In the interests of pursuing the development of new wear-resistant alloys, the current study was undertaken to investigate the effects of Mg additions ranging from 6 to 15 pct on the solidification behavior of hypereutectic Al-15Si-4Cu-Mg alloy using thermodynamic calculations, thermal analysis, and extensive microstructural examination. The Mg level strongly influenced the microstructural evolution of the primary Mg₂Si phase as well as the solidification behavior. Thermodynamic predictions using ThermoCalc software reported the occurrence of six reactions, comprising the formation of primary Mg₂Si; two pre-eutectic binary reactions, forming either Mg₂Si + Si or Mg₂Si + α-Al phases; the main ternary eutectic reaction forming Mg₂Si + Si + α-Al; and two post-eutectic reactions resulting in the precipitation of the Q-Al₅Mg₈Cu₂Si₆ and θ-Al₂Cu phases, respectively. Microstructures of the four alloys studied confirmed the presence of these phases, in addition to that of the π-Al₈Mg₃FeSi₆ (π-Fe) phase. The presence of the π-Fe phase was also confirmed by thermal analysis. The morphology of the primary Mg₂Si phase changed from an octahedral to a dendrite form at 12.52 pct Mg. Any further Mg addition only coarsened the dendrites. Image analysis measurements revealed a close correlation between the measured and calculated phase fractions of the primary Mg₂Si and Si phases. ThermoCalc and Scheil calculations show good agreement with the experimental results obtained from microstructural and thermal analyses.     

Quenching Differential Thermal Analysis and Thermodynamic Calculation to Determine Partition Coefficients of Solute Elements in Simplified Ni-Base Superalloys

In this article, a profile-fitting methodology was developed to measure the partition coefficients of solute elements during the solidification of Ni-base alloys. Better agreement with the theoretically calculated values is expected if the accuracy of the composition and the homogeneity of the model alloys are enhanced. Regular differential thermal analysis (DTA) measurements were consistently higher than the theoretical transition temperatures, and the differences were smaller when compared to the predictions performed with the thermodynamical database developed by Du et al. The better agreement between the experimental results and the theoretical predictions made with the newly developed database suggests that improvements in the accuracy of the theoretical predictions can still be obtained and are necessary for accurate freckling prediction. Quenching modified DTA (MDTA) experiments were proven to be appropriate for directly measuring the average partition coefficients of the solute elements. Regarding the cooling rate of the first stage of the quenching experiments, it was assumed successfully that the cooling rate prior to the quenching step of 0.083 Ks⁻¹ was sufficiently slow to permit easy quenching, while being fast enough for the primary solidification reaction to depart from the equilibrium model and being closer to the Scheil model of segregation. The minimization of the error function defined from the Scheil equation was found to be an appropriate method for describing the segregation profiles of the quenched samples and permitted good estimations of the partition coefficients of the solute elements. The reliability of the methodology was found to be satisfactory given that the magnitudes calculated for the partition coefficients of the solutes in the multicomponent alloy 718 were found to be very close to the values reported in the literature.