Liquid separation effects in Fe−Cu alloys solidified under different cooling rates

The effect of cooling rates on the microstructure of Fe−Cu alloys was investigated. A variety of solidification techniques was employed, in order to obtain a wide range of cooling rates. At high cooling rates (about 10⁴ K/sec), and in the composition range 30 to 80 wt pct Cu, the microstructures showed clear evidence of metastable liquid separation. This indicates a melt supercooling of about 50 to 100 K. Liquid separation coupled with high interfacial velocities resulted in solute trapping, and in a spherical morphology for one of the solids. At cooling rates lower than 10⁴ K/sec no liquid separation was observed, and the alloys solidified in a conventional manner,i.e., with a polycrystalline or a dendritic microstructure, depending on the Cu content. The type of the γ-Fe to α-Fe solid state transformation, taking place during cooling after solidification, depends on the cooling rates as well as on the Cu content in the γ-Fe phase. At medium cooling rates the transformation is martensitic, while at low or high cooling rates a polycrystalline transformed structure is obtained. A. MUNITZ, formerly Visiting Research Associate at the University of Florida at Gainesville, FL 32611     

Characterization of the peritectic reaction in medium-alloy steel through microsegregation and heat-of-transformation studies

In the present work, the phenomenon of the peritectic reaction was characterized in a medium-alloy steel. Several directional solidifcation and thermal-analysis experiments were done to investigate the reaction process. Directional solidification experiments carried out did not tend to show any direct evidence of a peritectic reaction. Microsegregation studies on the directionally solidified samples and those solidified under isothermal conditions bring out some interesting features. It has been documented that if the segregation ratio for Ni is higher than that for Cr, there is a correlation that the peritectic reaction had occurred in that region. On the other hand, a higher Cr segregation ratio as compared to Ni showed the possibility that the liquid had directly transformed to γ-austenite without undergoing a peritectic reaction. Measurement of energies of transformations and the analysis of their values in different segments of the cooling-curve differential thermal analysis (DTA) experiments have helped in understanding the peritectic reaction. It is revealed that the transformation is more like diffusionless transformation, where γ-austenite directly precipitates from δ-ferrite. Indeed, this proposition is also supported by the segregation patterns for Cr and Ni obtained in the solidified samples of this steel during directional solidifcation and DTA experiments and also by calculations to show the presence of enough lattice defects or vacancies to aid the aforementioned transformation.     

冷却速率对δ-TRIP钢包晶相变的影响

在钢的凝固过程中冷却速率对钢的相变具有不可忽视的影响。本研究采用Thermo-calc热力学软件,模拟计算了含Al 3.52%（质量分数）的δ铁素体相变诱导塑性（δ-TRIP）钢的相转变过程,并分别使用差示扫描量热法（DSC)和Ohnaka微观偏析模型,分析了不同冷却速率对3.52%Al δ-TRIP钢凝固过程中的包晶相变温度,以及溶质元素偏析的影响。结果表明,冷却速率越小,DSC试验所得的相变温度越接近Thermo-calc计算的热力学平衡值。随着冷却速率从10、30增加到50 ℃·min–1,L→L+δ的转变温度降低,L+δ→L+δ+γ和L+δ+γ→δ+γ的转变温度先降低后升高,前者主要受过冷度的影响,后者主要受元素偏析的影响。冷却速率对C、Mn、S的偏析影响很小,对Si、P、Al的偏析影响较大,并且随着冷却速率的增加,Si、P、Al偏析程度增加。Si和P的偏析会小幅度延缓包晶反应的进程;Al对改变包晶反应进程作用明显,随着冷却速率的增加,包晶反应区域逐渐下移,且下移趋势渐缓。      

FeS-MnS phase relationships in the presence of excess iron

The FeS-MnS system is reexamined, both with and without excess iron. When excess iron is present, as is true for sulfide inclusions within steel, the pseudobinary reveals a peritectic rather than the previously assumed eutectic invariant. The maximum solubility limits (997 ± 3°C, or 1270 K) in the two solid phases are: a) 7.5 wt pct MnS in FeS, and b) 73.5 wt pct FeS in MnS. The peritectic liquid contains 66 wt pct Fe, ∼34 wt pct S, and ∼0.4 wt pct Mn. The two solid sulfide phases are nearly stoichiometric in the presence of excess iron; the Fe-richer sulfide is metal-deficient in the absence of a metallic iron phase. Based on this study, it is possible to be more specific than heretofore about the Fe-FeS-MnS-Mn region of the Fe-Mn-S ternary. In addition to the presence of a peritectic, it was concluded that the miscibility gap does not cross the univariant line between primary metal and (Mn,Fe)S phases. The peritectic liquid and the Mn-richer solid sulfide equilibrate with a metal containing ≤ 0.36 wt pct Mn. These data help explain the Mn/s ratios required to avoid hot-shortness in regular and resulfurized plain-carbon steels. G. S. MANN, formerly Graduate Student This is a part of the dissertation submitted by G. S. Mann for his Ph.D. at the University of Michigan     

Solidification of undercooled Sn-Sb peritectic alloys: Part I. Microstructural evolution

The droplet emulsion technique, which involves dispersal of a bulk liquid alloy into a collection of fine droplets (5 to 30μm), was applied to Sn-Sb alloys to yield high levels of controlled undercooling. The maximum undercooling levels achieved varied from 179 °C for pure Sn to 113 °C for a Sn-16 at. pct Sb alloy. Analysis of hypoperitectic alloy samples (alloys with an Sb content less than that of the liquid at the peritectic temperature) indicates that solute trapping occurs during solidification at the levels of undercooling and cooling rate investigated, yielding nearly homogeneousβ-tin solid solutions with compositions approaching those of the bulk alloys. With increasing undercooling and/or cooling rate, hyperperitectic alloys exhibit a transition from a highly segregated structure consisting of faceted primary intermetallic phase and cellularβ to a structure consisting primarily of a supersaturated tin-rich solid solution. Lattice constant measurements confirm that virtually complete supersaturation ofβ-tin was achieved in emulsion samples cooled at 200 °C s^s−1 for compositions up to approximately 20 at. pct Sb. The development and characteristics of subsequent solid-state precipitation were used to guide the interpretation of the often complex solidification reaction sequences in the hyperperitectic alloys. The formation of supersaturatedβ-tin solid solutions in the undercooled samples is related to the appropriate metastable phase equilibria and the development of solute trapping. Formerly Graduate Student, Department of Materials Science and Engineering, University of Wisconsin-Madison     

微合金钢连铸坯表面裂纹敏感性预测模型

为了从凝固及相变特性角度解决微合金钢连铸坯表面裂纹问题,建立了与合金化相关联的初始凝固包晶反应度模型、奥氏体晶粒长大模型、铁素体转变量模型以及碳氮化物的析出模型。结合铸坯实际冷却条件,进一步建立了包晶反应度预测、初生奥氏体晶粒长大、铁素体转变、析出相析出等对铸坯表面裂纹敏感性的预测模型。针对某J55钢连铸板坯,奥氏体晶粒尺寸超过1 mm、铁素体析出量为10%、二次相析出量增加时,横裂纹敏感性最大。表面裂纹敏感性预测模型有助于实现基于成分微调和组织调控的微合金钢连铸、热装等生产过程表面裂纹控制技术。     

Nonequilibrium Solidification Behavior of Co-Si Alloys Near the First Eutectic Point

Adopting a fluxing purification and cyclic superheating technique, Co-10 wt pct Si and Co-15 wt pct Si alloys had been undercooled to realize rapid solidification in this work. It was investigated that the solidification modes and microstructures of Co-Si alloys were deeply influenced by the undercooling of the melts. Both alloys solidified with a near-equilibrium mode in a low undercooling range; the peritectic reaction occurred between the primary phase and the remnant liquids, and it was followed by the eutectic reaction and eutectoid transformation. With the increase of undercooling, both alloys solidified with a nonequilibrium mode, and the peritectic reaction was restrained. As was analyzed, a metastable Co₃Si phase was found in Co-10 wt pct Si alloy when a critical undercooling was achieved.     

包晶钢结晶器液面周期性波动原因及控制

针对鞍钢股份有限公司鲅鱼圈钢铁分公司板坯连铸在生产包晶系列钢种时．连铸结晶器钢液面周期性剧烈波动的原因进行了分析。包晶钢液在凝固过程的包晶相变造成初生坯壳的不均匀生长是导致结晶器出现液面周期性剧烈波动的主要原因。通过调整结晶器冷却水强度和控制保护渣传热性能,有效地控制了结晶器液面周期性波动,提高了铸坯质量。     

The solidification characteristics of Fe-rich intermetallics in Al-11.5Si-0.4Mg cast alloys

After the nucleation and sedimentation of primary Fe-rich phases, the microstructures of Al-11.5Si-0.4Mg cast alloys with 0.35–1.03Fe and 0.18–0.59Mn have been studied to investigate the solidification characteristics of Fe-rich phases. Depending on the iron and manganese contents as well as cooling rates, Fe-rich phases may solidify as predendritic (primary), pre-eutectic, coeutectic, and posteutectic intermetallics at the different stages of solidification through three types of reactions: (1) predendritic (primary), (2) eutectic, and (3) peritectic reactions. It seems that Fe-rich phases may nucleate on the wetted sides of double oxide films, while the gap of the dry sides of oxide films constitutes the cracks commonly observed in the Fe-rich phases and aluminum matrix. Conventional metallurgical observations also suggest that the Fe-rich phases nucleated early during the solidification might act as nuclei for those formed subsequently, although it has not been ruled out that these phases may share the same oxide substrates. It is probable that these nucleation events may all work as suggested in the possible nucleation hierarchy for Al-11.5Si-0.4Mg cast alloys.     

钢凝固过程中二次枝晶间溶质分布的模型研究

对凝固过程中二次枝晶间溶质质量分数分布进行了模型研究，该模型考虑了包晶反应的影响以及固相中溶质的扩散，讨论了钢中w（C）以及冷却速度对枝晶间溶质质量分数分布的影响。计算结果表明，枝晶间Mn、P的偏析较严重，随着w（C）的增加，枝晶间Mn、P的偏析加剧，随着冷却速度的降低，枝晶间P的偏析降低。     

Determination of Solid Fraction from Cooling Curve

A new method to determine directly the solid fraction using the cooling curve was proposed for solidification of undercooled melts. Then, to construct three different baselines, a sudden function ξ _α (x) is introduced. In terms of the ξ _α (x) function, accordingly, the solid fractions during solidification of Ni-3.3 wt pct B, Al-7 wt pct Si, Al-14 wt pct Cu, and Fe-4.56 wt pct Ni alloys were predicted. The predictions of the primary, the regular lamellar eutectic, the anomalous eutectic, and the peritectic phases from cooling curves of the solidified samples coincide with the results of measurement or the available methods.     

Thermal Analysis and Microstructure of ZA8 Alloy Solidifying Against Chills

Thermal analysis during solidification of ZA8 alloy against copper, hot die steel and stainless steel chills instrumented with thermocouples was carried out in the present work. The investigation showed that the chill material and coating had a significant effect on the cooling curve of the casting. When casting was solidified against chills, the liquidus and eutectic start temperature of the casting remained nearly the same whereas eutectoid transformation occurred at a higher temperature. Cooling rate curve of the casting solidified against coated chill indicated that formation of solid shell and subsequent re-melting in the case of high thermal conductivity coated chill whereas in lower thermal conductivity coated chill, the re-melting of solid shell was absent. It was found that chilling during solidification causes the morphology of dendrites transform to nearly rounded shape with refinement of lamellar eutectic.     

Modeling of the peritectic reaction and macro-segregation in casting of low carbon steel

Macro-microscopic models have been developed to describe the macrosegregation behavior associated with the peritectic reaction of low carbon steel. The macrosegregation model has been established on the basis of previously published work and experimental data. A microscopic model of a three-phase reaction L+δ→γ has been modeled by using Fredriksson’s approach. Four horizontal and unidirectional solidified experimental groups simulating continuous casting have been performed with a low carbon steel containing 0.13 wt pct carbon. The extent of macrosegregation of carbon was determined by wet chemical analysis of millings. It is confirmed, by comparing calculated results with experimental results, that this model successfully predicts the occurrence of macrosegregation. The results indicate that a peritectic reaction which is associated with a high cooling rate generates high thermal contraction and a high tensile strain rate at the peritectic temperature. Therefore, the macrosegregation, particularly at the ingot surface, is very sensitive to the cooling rate, where extremely high positive segregation was observed in the case of a high cooling rate. However, in the case of slow cooling rate, negative segregation was noted. The mechanism of macrosegregation with peritectic reaction is discussed in detail.     

Effects of Undercooling and Cooling Rate on Peritectic Phase Crystallization Within Ni-Zr Alloy Melt

The liquid Ni-16.75 at. pct Zr peritectic alloy was substantially undercooled and containerlessly solidified by an electromagnetic levitator and a drop tube. The dependence of the peritectic solidification mode on undercooling was established based on the results of the solidified microstructures, crystal growth velocity, as well as X-ray diffraction patterns. Below a critical undercooling of 124 K, the primary Ni₇Zr₂ phase preferentially nucleates and grows from the undercooled liquid, which is followed by a peritectic reaction of Ni₇Zr₂+L → Ni₅Zr. The corresponding microstructure is composed of the Ni₇Zr₂ dendrites, peritectic Ni₅Zr phase, and inter-dendritic eutectic. Nevertheless, once the liquid undercooling exceeds the critical undercooling, the peritectic Ni₅Zr phase directly precipitates from this undercooled liquid. However, a negligible amount of residual Ni₇Zr₂ phase still appears in the microstructure, indicating that nucleation and growth of the Ni₇Zr₂ phase are not completely suppressed. The micromechanical property of the peritectic Ni₅Zr phase in terms of the Vickers microhardness is enhanced, which is ascribed to the transition of the peritectic solidification mode. To suppress the formation of the primary phase completely, this alloy was also containerlessly solidified in free fall experiments. Typical peritectic solidified microstructure forms in large droplets, while only the peritectic Ni₅Zr phase appears in smaller droplets, which gives an indication that the peritectic Ni₅Zr phase directly precipitates from the undercooled liquid by completely suppressing the growth of the primary Ni₇Zr₂ phase and the peritectic reaction due to the combined effects of the large undercooling and high cooling rate.     

Kinetics of the peritectic phase transformation: In-situ measurements and phase field modeling

An experimental study has been conducted into the role of cooling rate on the kinetics of the peritectic phase transformation in a Fe-C alloy. The interfacial growth velocities of the peritectic phase transformation were measured in situ for cooling rates of 100, 50, and 10 K/min. In-situ observations were obtained using high-temperature laser scanning confocal microscopy (HTLSCM) in a concentric solidification configuration. The experimentally measured interface velocities of the liquid/austenite (L/γ) and austenite/delta-ferrite (γ/δ) interphase boundaries were observed to increase with higher cooling rates. A unique finding of this study was that as the cooling rate increased, there was a transition point where the L/γ interface propagated at a higher velocity than the γ/δ interface, contrary to the findings of previous researchers. Phase field modeling was conducted using a commercial multicomponent, multiphase package. Good correlation was obtained between model predictions and experimental observations in absolute values of interface velocities and the effect of cooling rate. Analysis of the simulated microsegregation in front of the L/γ and γ/δ interfaces as a function of cooling rate revealed the importance of solute pileup. This microsegregation plays a pivotal role in the propagation of interfaces; thus, earlier modeling work in which complete diffusion in the liquid phase was assumed cannot fully describe the rate of propagation of the L/γ and δ/γ interfaces during the course of the peritectic transformation.     

中锰钢高温热塑性研究

摘要：采用真空感应炉熔炼中锰钢,经铸铁模冷却至室温铸锭内部存在大量的微观裂纹,实验表明中锰钢高温热塑性极差。而采用铸铁模冷却至700℃后,置于700℃马弗炉随炉冷却至室温铸锭内部微观裂纹消失。将试样经过热轧锻造后,中锰钢的热塑性较为良好。研究表明铸锭中柱状晶发达以及凝固过程产生的微观裂纹是造成热塑性极差的主要原因,铸铁模快冷引起的热应力和铸锭完全凝固700℃以后相变应力是造成铸坯内部裂纹的主要因素。生产过程推荐采用结晶器、二冷段相对弱冷工艺措施降低铸坯产生裂纹风险性。     

Kinetics of the peritectic phase transformation: In-situ measurements and phase field modeling

An experimental study has been conducted into the role of cooling rate on the kinetics of the peritectic phase transformation in a Fe−C alloy. The interfacial growth velocities of the peritectic phase transformation were measured in situ for cooling rates of 100, 50, and 10 K/min. In-situ observations were obtained using high-temperature laser scanning confocal microscopy (HTLSCM) in a concentric solidification configuration. The experimentally measured interface velocities of the liquid/austenite (L/γ) and austenite/delta-ferrite (γ/δ) interphase boundaries were observed to increase with higher cooling rates. A unique finding of this study was that as the cooling rate increased there was a transition point where the L/γ interface propagated at a higher velocity than the γ/δ interface, contrary to the findings of previous researchers. Phase field modeling was conducted using a commercial multicomponent, multiphase package. Good correlation was obtained between model predictions and experimental observations in absolute values of interface velocities and the effect of cooling rate. Analysis of the simulated microsegregation in front of the L/γ and γ/δ interfaces as a function of cooling rate revealed the importance of solute pileup. This microsegregation plays a pivotal role in the propagation of interfaces; thus, earlier modeling work in which complete diffusion in the liquid phase was assumed cannot fully describe the rate of propagation of the L/γ and δ/γ interfaces during the course of the peritectic transformation.     

Kinetics of the peritectic phase transformation: In-situ measurements and phase field modeling

An experimental study has been conducted into the role of cooling rate on the kinetics of the peritectic phase transformation in a Fe−C alloy. The interfacial growth velocities of the peritectic phase transformation were measuredin situ for cooling rates of 100, 50, and 10 K/min.In-situ observations were obtained using high-temperature laser scanning confocal microscopy (HTLSCM) in a concentric solidification configuration. The experimentally measured interface velocities of the liquid/austenite (L/γ) and austenite/delta-ferrite (γ/δ) interphase boundaries were observed to increase with higher cooling rates. A unique finding of this study was that as the cooling rate increased there was a transition point where the L/γ interface propagated at a higher velocity than the γ/δ interface, contrary to the findings of previous researchers. Phase field modeling was conducted using a commercial multicomponent, multiphase package. Good correlation was obtained between model predictions and experimental observations in absolute values of interface velocities and the effect of cooling rate. Analysis of the simulated microsegregation in front of the L/γ and γ/δ interfaces as a function of cooling rate revealed the importance of solute pileup. This microsegregation plays a pivotal role in the propagation of interfaces; thus, earlier modeling work in which complete diffusion in the liquid phase was assumed cannot fully describe the rate of propagation of the L/γ and δ/γ interfaces during the course of the peritectic transformation.     

Solidification of M2 high speed steel

The freezing process in AISI type M2 high speed tool steel (6 pct W, 5 pct Mo, 4 pct Cr, 2 pct V, 0.8 pct C) was studied by metallographic and thermal analysis techniques. Unidirectional solidification of small laboratory melts in a modified crystal growing apparatus was employed to provide metallographic sections of known macroscopic growth direction. Also cooling curves were obtained on 40 g specimens solidified in thimble crucibles. X-ray microradiography, electron probe scanning techniques, and quantitative microanalysis of dendrites and interdendritic carbides were extensively used to supplement conventional metallography. Carbon and vanadium contents of M2 were varied in order to observe the effect of an austenite and ferrite stabilizer on the thermal analysis curves and microstructure. The nonequilibrium freezing process in M2 includes three major liquid-solid reactions: 1) Liquid → Ferrite, 1435°C; 2) Liquid + Ferrite → Austenite, 1330°C; 3) Liquid → Austenite + M₆C + MC, 1240°C. These reactions account for the as-cast structure of the commercial alloy. The addition of carbon depresses the liquidus (1) and solidus temperatures (3) and narrows the gap between the liquidus (1) and peritectic transformation (2). This gap is eliminated at > 1.39 wt pct C, where the initial freezing reaction is the crystallization of austenite. The accompanying microstructural change is the elimination of σ eutectoid dendrite cores. The addition of vanadium promotes ferrite formation by strongly depressing the peritectic reaction and thus widening the gap between the liquidus and the peritectic.     

第3代汽车钢凝固过程微观偏析的耦合模型

基于Clyne-Kurz的微观偏析公式,以物理试验结果为依据,充分考虑固、液相以及夹杂物之间相互作用,建立第3代汽车钢(TG钢)凝固过程微观偏析耦合模型,研究凝固过程钢液中溶质元素和Al2O3等夹杂物分子的质量分数变化特征。结果表明:在整个凝固过程中,Al2O3分子会不断在液相中生成,但生成量比较少,而SiO2和MnO分子不会在液相中生成;铸坯枝晶间不仅有Al2O3夹杂,还有SiO2和其他复合夹杂,凝固前钢水中夹杂物有待进一步去除;凝固末期液相中MnS析出,大大减小了残余液相中S的质量分数变化,但对Mn的质量分数变化没有明显影响;包晶反应温度为1 487℃,包晶反应后凝固的固相中溶质的质量分数明显高于包晶反应前。