成分与冷却速率对高硅不锈钢凝固模式的影响

 高硅奥氏体不锈钢因其较高的Si元素含量所表现出的优异耐蚀性能而成为制酸行业普遍应用的一种特殊钢种。然而,高含量Si元素的加入会引发铸造缺陷和成分偏析加剧以及钢中析出相增多,热加工过程中易产生热裂纹等问题。高硅奥氏体不锈钢凝固过程中δ铁素体的含量、形态和分布与合金化学成分和热加工历史紧密相关,其室温组织取决于析出相的析出顺序和随后的固态相变,因此,奥氏体不锈钢的凝固模式势必会影响合金的热塑性。为此通过调整高硅奥氏体不锈钢中Si元素与Cr元素的含量,采用金相显微镜(OM)、X射线衍射仪(XRD)、扫描电镜能谱分析(SEM/EDS)、电子探针(EPMA)、JMatPro软件计算等方法,探究了合金成分变化与冷却速率对高硅奥氏体不锈钢凝固模式的影响,并对经典铬镍当量算法进行了评估。结果表明,Schneider铬镍当量算法相较于Rajasekhar铬镍当量算法对大多数合金的凝固模式预测较为准确;随着合金中Si元素与Cr元素含量的提高,合金凝固模式由AF模式转变为FA模式,合金凝固过程中经历更多的“δ→γ”固态相变,其中质量分数为6.0%Si成分的合金对应的δ铁素体增幅减缓;随着质量分数为5.0%的Si铸锭冷却速率的提高,合金凝固模式由AF模式转变为A模式;Hammar and Svensson凝固路线判据可以准确预测高硅奥氏体不锈钢的初始析出相。研究为合理制定高硅奥氏体不锈钢的合金成分与成形工艺提供理论依据。     

铜锡合金激光选区熔化非平衡凝固组织与性能

对具有重要工程应用价值的Cu?5%Sn合金进行激光选区熔化（SLM）成形,在激光功率160 W、扫描速度300 mm·s?1、扫描间距0.07 mm条件下,合金样品相对密度可达99.2%,熔池层与层堆积密实,表面质量良好。研究发现所获合金具有非平衡凝固组织特征,其中以α-Cu(Sn)固溶体相为主,且涉及具有超结构的γ相、δ相。显微形貌主要由柱状晶与富锡网状组织构成,伴随有不同尺度界面Sn元素偏析及晶界、晶内纳米尺寸超结构合金相颗粒析出。所获合金的力学性能与同成分铸态合金或较低Sn含量SLM合金相比得到显著强化,表面硬度可达HV 133.83,屈服强度326 MPa,抗拉强度387 MPa及断裂总延伸率22.7%。      

Solidification modeling and solid-state transformations in high-energy density stainless steel welds

The solidification and solid-state transformations which occur during the high-energy density (HED) welding of austenitic stainless steel were studied. Comparisons were made between structures observed in gas tungsten arc (GTA) welds and those of electron beam (EB) and laser welds using Fe-Ni-Cr ternary alloys with Cr/Ni ratios ranging from 1.5 to 1.85. Weld solidification and microsegregation was modeled using a finite difference analysis and compared with experimental results. These calculations were also used to help interpret the origin of the observed microstructures. Calculations showed that little solid-state diffusion occurs during the solidification and cooling of primary austenite solidified welds, whereas structures which solidify as ferrite may become almost completely homogenized as a result of diffusion. A change in solidification mode from primary austenite to primary ferrite was found to occur at higher Cr/Ni ratios with the HED welds than with GTA welds and is attributed to dendrite tip undercooling. A nearly segregation-free, single-phase austenite structure which appears to be unique to the rapid solidification velocities and cooling rates of HED welds was also observed. It is suggested that this structure is a product of ferrite solidification which transforms to austenitevia a massive transformation.     

An Investigation of the Massive Transformation from Ferrite to Austenite in Laser-Welded Mo-Bearing Stainless Steels

A series of 31 Mo-bearing stainless steel compositions with Mo contents ranging from 0 to 10 wt pct and exhibiting primary δ-ferrite solidification were analyzed over a range of laser welding conditions to evaluate the effect of composition and cooling rate on the solid-state transformation to γ-austenite. Alloys exhibiting this microstructural development sequence are of particular interest to the welding community because of their reduced susceptibility to solidification cracking and the potential reduction of microsegregation (which can affect corrosion resistance), all while harnessing the high toughness of γ-austenite. Alloys were created using the arc button melting process, and laser welds were prepared on each alloy at constant power and travel speeds ranging from 4.2 to 42 mm/s. The cooling rates of these processes were estimated to range from 10 K (°C)/s for arc buttons to 10⁵ K (°C)/s for the fastest laser welds. No shift in solidification mode from primary δ-ferrite to primary γ-austenite was observed in the range of compositions or welding conditions studied. Metastable microstructural features were observed in many laser weld fusion zones, as well as a massive transformation from δ-ferrite to γ-austenite. Evidence of epitaxial massive growth without nucleation was also found when intercellular γ-austenite was already present from a solidification reaction. The resulting single-phase γ-austenite in both cases exhibited a homogenous distribution of Mo, Cr, Ni, and Fe at nominal levels.     

Nucleation and phase selection in undercooled Fe-Cr-Ni melts: Part I. Theoretical analysis of nucleation behavior

The selection of the primary solidifying phase in undercooled stainless steel melts is theoretically analyzed in terms of nucleation theory. Nucleation phenomena are considered using different models for the solid-liquid interface energy. The classical nucleation theory for sharp interfaces and an improved modification, the diffuse interface theory, are applied. The influence of deviations of the nucleus composition from the overall alloy composition is also revealed. A preferred nucleation of the metastable bcc phase in fcc equilibrium solidification-type alloys is predicted. The critical undercooling of metastable crystallization as a function of alloy composition is calculated for an isoplethal section at 69 at. pct Fe of Fe₆₉Cr_31-x Ni _x alloys. The results are summarized in a phase selection diagram predicting the primary solidification mode as a function of undercooling and melt composition.     

Microstructures of Austenitic Stainless Steel Produced by Twin-Roll Strip Caster

 The microstructures of austenitic stainless steel strip were studied using color metallographic method and electron probe micro analysis (EPMA). In the cast strips, there are three kinds of solidification structures: fine cellular dendrite in the surface layer, equiaxed grains in the center and fine dendrite between them. The solidification mode in the surface layer is the primary austenite AF mode because of extremely high cooling rate, with the retained ferrite located around the primary cellular austenite. In the fine dendrite zone, the solidification mode of molten stainless steel changes to FA mode and the residual ferrite with fish-bone morphology is located at the core of the dendrite. The retained ferrite of equiaxed grains in the center is located in the center of broken primary ferrite dendrite with vermicular morphology.     

Microstructural transitions during containerless processing of undercooled Fe-Ni alloys

The microstructural development associated with solidification in undercooled Fe-Ni alloys has been reported in different studies to follow various pathways, with apparent dissimilarities existing as a function of sample size and processing conditions. In order to identify the possible hierarchy of microstructural pathways and transitions, a systematic evaluation of the microstructural evolution in undercooled Fe-Ni alloys was performed on uniformly processed samples covering seven orders of magnitude in volume. At appropriate undercooling levels, alternate solidification pathways become thermodynamically possible and metastable product structures can result from the operation of competitive solidification kinetics. For thermal history evaluation, a heat flow analysis was applied and tested with large Fe-Ni alloy particles (1 to 3 mm) to assess undercooling potential. Alloy powders (10 to 150 μm), with large liquid undercoolings, were studied under the same composition and processing conditions to evaluate the solidification kinetics and microstructural evolution, including face-centered cubic (fcc)/body centered cubic (bcc) phase selection and the thermal stability of a retained metastable bcc phase. The identification of microstructural transitions with controlled variations in sample size and composition during containerless solidification processing was used to develop a microstructure map which delineates regimes of structural evolutions and provides a unified analysis of experimental observations in the Fe-Ni system.     

Examination of solidification pathways and the liquidus surface in the Nb-Ti-Al system

The solidification pathways, subsequent solid-state transformations, and the liquidus surface in the Nb-Ti-Al system have been examined as part of a larger investigation of phase equilibria in Nb-Ti-Al intermetallic alloys. Fifteen alloys ranging in composition from 15 to 40 at. pct Al, with Nb to Ti ratios of 4:1, 2:1, 1.5:1, 1:1, and 1:1.5, were prepared by arc melting and the as-cast microstructures were characterized by optical microscopy (OM), microhardness, X-ray diffraction (XRD), differential thermal analysis (DTA), backscattered electron imaging (BSEI), electron probe microanalysis (EPMA), and transmission electron microscopy (TEM). The results indicate that the range of primary β solidification is much wider than that indicated in previously reported liquidus surfaces, both experimental and calculated. Differential thermal analysis has identified the existence of a β to σ+γ transformation in three alloys where it was previously thought not to exist; confirmation was provided by high-temperature vacuum heat treatments in the single-phase β region followed by rapid quenching. The location of the boundary between the β, σ, and δ primary solidification fields has been redefined. A massive β → δ transformation, which was observed in the cast microstructure of a Nb-25Ti-25Al alloy, was repeatable through cooling following homogenization. A β → δ+σ eutectoid-like transformation in the 25 at. pct Al alloys, was detected by DTA and evaluated through microstructural analysis of heat-treated samples. Trends in the β phase with variations in composition were established for both lattice parameters and microhardness. As a result of this wider extent of the primary β solidification field, a greater possibility exists for microstructural control through thermal processing for alloys consisting of either σ+γ, β+σ, or β+δ phases. An erratum to this article is available at .     

Solidification mechanism of martensitic stainless steel

Abstract

In an unidirectional solidification experiment, an 8 kg stainless steel ingot with the composition 0·25%C, 17%Cr, and 1%Mn was solidified under continuous casting conditions. The dwell time of primary cooling was varied, followed by secondary spray cooling. Metallographic investigation, heat transfer, and segregation were carried out to study the solidification mechanism. The partition ratio of the elements present in ferrite and in austenite (martensite) was determined. It was indicated that the solidification follows: L → L + δ → L + δ + γ → δ + γ + carbides. Under high cooling rates γ austenite solidifies as a leading phase. The beginning of spray cooling has the main effect in controlling the obtained microstructures. Carbide thickening is observed in the rapidly cooled zone between the ferrite and the martensitic matrix. Tempered martensite increases by lowering the cooling rate, which gives more time for carbide dissolution and for carbon to diffuse into the ferrite, eventually increasing the austenite (martensite) fraction in the final matrix at the expense of ferrite.     

Two-Zone Microstructures in Al-18Si Alloy Powders

Hypereutectic Al-18 wt pct Si alloy is widely used in automotive industry as a wear-resistant alloy for engine components. However, in the last few years, this traditional composition is being considered for processing by different rapid solidification methods. Positive points include its low thermal expansion and uniform distribution of surface oxides. Nevertheless, the microstructural aspects of Al-Si powders of 18 wt pct Si are still need to be addressed, such as, the eutectic Si morphology, size, and distribution generated by different process conditions during rapid solidification. Based on a detailed quantitative analysis of the microstructures of rapid solidified Al-18 wt pct Si in this work, solidification conditions that yield specific Si morphologies, Si spacing, and thermal cooling conditions are outlined. The focus is determining the solidification conditions that will yield a specified shape of eutectic Si. It is shown that Si morphology is dependent on a combination of growth velocity (based on modified JH model) and temperature gradient. Furthermore, the highest hardness is achieved with globular morphologies of Si. The processing conditions required to achieve these properties are outlined.     

Modeling of irregular eutectic microstructures in solidification of Al-Si alloys

A modified cellular automaton (MCA) model was developed and applied to simulate the evolution of solidification microstructures of both eutectic and hypoeutectic Al-Si alloys. The present MCA model considers the equilibrium and metastable equilibrium solidification processes in a multiphase system. It accounts for the aspects including the nucleation of a new phase, the growth of primary α dendrites and two eutectic solid phases from a single liquid phase, as well as the coupling between the phase transformation and solute redistribution in liquid. The effects of alloy composition and eutectic undercooling on eutectic morphology and eutectic nucleation mode were investigated. The simulated results were compared with those obtained experimentally.     

The role of phase transformation in electron-beam welding of TiAl-based alloys

The weldability of two TiAl-based alloys, Ti-45Al-2Nb-2Mn and Ti-48Al-2Nb-2Mn, was investigated with the electron-beam welding process. It was found that the alloys were susceptible to solid-state cracking due to high thermally induced stresses and, more significantly, to the intrinsic brittleness of the microstructures. This work correlated the quality of the TiAl welds, made using different sets of welding parameters which gave rise to different cooling rates, to the microstructures that developed during welding. It was found that the welds were crack-free if the weld cooling rates were such that decomposition of the high-temperature α phase in the weld was not suppressed. It was shown that the Ti-48Al-based alloy was less susceptible to the solid-state cracking and, thus, was more weldable than the Ti-45Al-based alloy because the α phase in the alloy with a higher aluminum content could decompose more readily. A continuous cooling transformation (CCT) diagram is suggested to be used as an appropriate reference for the selection of welding parameters which induce suitable microstructures in the welds and result in crack-free welds.     

Microstructure and Phase Formation in a Rapidly Solidified Laser-Deposited Ni-Cr-B-Si-C Hardfacing Alloy

In this study, microstructural evolutions and phase selection phenomena during laser deposition of a hardfacing Ni-Cr-B-Si-C alloy at different processing conditions are experimentally investigated. The results show that even minor variations in the thermal conditions during solidification can modify the type and morphology of the phases. Higher undercoolings obtained at faster cooling rates suppressed the primary borides and encouraged floret-shape mixtures of Ni and Cr₅B₃ via a metastable reaction. Variations in the boride phases are discussed in terms of nucleation- and growth-controlled phase selection mechanisms. These selection processes also influenced the nature and proportion of the Ni-B-Si eutectics by changing the amount of the boron available for the final eutectic reactions. The results of this work emphasize the importance of controlling the cooling rate during deposition of these industrially important alloys using laser beam or other rapid solidification techniques.     

Microstructural modification of austenitic stainless steels by rapid solidification

The microstructural modifications in three austenitic stainless steels (types 308, 310, and 312) were evaluated after rapid solidification. These three steels are commonly used weld filler metals. Two methods of rapid solidification were investigated, autogenous laser welding and arc-hammer splat quenching. The structure of 310 stainless steel was found to be 100 pct austenite, and did not vary over the range of conditions studied. On the contrary, the structures of types 308 and 312 steels were very sensitive to the cooling rates and solidification conditions. With the highest cooling rates, the type 308 structure was fully austenitic while the type 312 structure was fully ferritic. At lower cooling rates, the structures were duplex ferrite plus austenite. The results were interpreted in terms of faster kinetics of solidification of austenite compared to ferrite under the conditions examined. A comparison of the structures produced by the two rapid solidification techniques indicated the cooling rates are comparable.     

The Evolution of As-cast Microstructure of Ternary Mg-Al-Zn Alloys: An Experimental and Modeling Study

A numerical formulation of solidification model which can predict the microsegregation and microstructural features for multicomponent alloys is presented. The model incorporates the kinetic features during solidification such as solute back diffusion, dendrite tip undercooling, and secondary arm coarsening. The model is dynamically linked to thermodynamic library for accurate input of thermodynamic data. The modeling results are tested against the directional solidification experiments for Mg-Al-Zn alloys. The experiments were conducted in the cooling rate range of 0.13 to 2.33 K/s and microstructural features such as secondary arm spacing, primary dendrite arm spacing, second phase fraction, and microsegregation were compared with the modeling results. Based on the model and the experimental data, a solidification map was built in order to provide guidelines for as-cast microstructural features of Mg-Al-Zn alloys in a wide range of solidification conditions.     

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.     

Microstructural and microhardness characteristics of laser-synthesized Fe-Cr-W-C Coatings

The effects of laser-processing parameters on the microstructure and microhardness of Fe-Cr-W-C quaternary alloy coatings were investigated experimentally. The coatings were developed by laser processing a powder mixture of Fe, Cr, W, and C at a weight ratio of 10:5:1:1 on a low-carbon steel substrate using a 10 kW continuous wave CO₂ laser. Depending on the processing parameters, either hypoeutectic or hypereutectic microstructures were produced. The hypoeutectic microstructures comprised primary dendrites of nonequilibrium face-centered cubic (fcc) austenite γ phase and eutectic consisting of pseudohexagonal close-packed (hcp) M₇C₃ (M = Cr, Fe, W) carbides and fcc γ phase. The hypereutectic microstructures consisted of hcp M₇C₃ primary carbides and eutectic similar to that in the hypoeutectic microstructures. The formation of hypoeutectic or hypereutectic microstructures was influenced by the alloy composition, particularly the C concentration, which depends on the amount of powder delivered into the melt pool and the extent of substrate melting. The enhancement of the lattice parameter of the γ phase is associated with the significant dissolution of alloying elements and lattice strains resulting from rapid quenching. The higher hardness of the hypereutectic microstructures is principally attributed to the formation of hcp M₇C₃ primary carbides. The relatively lower hardness of the hypoeutectic microstructures is related to the presence of y phase in the primary dendrites, excessive dilution from the base material, and relatively low concentrations of Cr and C. The results provide insight into the significance of laser-processing conditions on the composition and hardness of Fe-Cr-W-C alloy coatings and associated solidification characteristics.