On the Role of Grain Boundary Serration in Simulated Weld Heat-Affected Zone Liquation of a Wrought Nickel-Based Superalloy

The effects of grain boundary serration on boron segregation and liquation cracking behavior in a simulated weld heat-affected zone (HAZ) of a wrought nickel-based superalloy 263 have been investigated. The serrated grain boundaries formed by the developed heat treatment were highly resistant to boron segregation; the serrated sample contained 41.6 pct grain boundaries resistant to boron enrichment as compared with 14.6 pct in the unserrated sample. During weld thermal cycle simulation, liquated grain boundaries enriched with boron were observed at the peak temperature higher than 1333 K (1060 °C) in both unserrated and serrated samples; however, serrated grain boundaries exhibited a higher resistance to liquation. The primary cause of liquation in this alloy was associated with the segregation of the melting point depressing element boron at grain boundaries. The hot ductility testing result indicated that the serrated grain boundaries showed a lower susceptibility to liquation cracking; the grain boundary serration led to an approximate 15 K decrease in the brittle temperature range. These results reflect closely a significant decrease in interfacial energy as well as a grain boundary configuration change by the serration.     

Sulfur segregation to grain boundaries in Ni3Al and Ni3(AI,Ti) alloys

The segregation of S to grain boundaries in Ni₃Al and Ni₃(Al, Ti) has been studied using Auger electron spectroscopy. The S concentration at the grain boundaries decreases more slowly with increasing temperature than would be predicted by segregation models based on a single solute binding energy to the grain boundaries. This behavior, which can be interpreted as an increase in the effective solute binding energy for a grain boundary as a function of temperature, is consistent with predictions of a model based on the existence of a spectrum of solute binding energies for grain boundaries. Formerly Professor and Head of the Department of Metallurgical Engineering, Michigan Technological University     

Effect of homogenization heat treatment on the microstructure and heat- affected zone microfissuring in welded cast alloy 718

The effect of homogenization temperature on microfissuring in the heat-affected zones of electronwelded cast INCONEL 718 has been studied. The material was homogenized at various temperatures in the range of 1037 ° to 1163 ° and air-cooled. The homogenized material was then electron-beam welded by the bead-on-plate welding technique. The microstructures and microfissuring in the heat-affected zone (HAZ) were evaluated by analytical scanning electron microscopy (SEM). The grain boundary segregation of various elements was evaluated by secondary ion mass spectroscopy (SIMS). It was observed that the total crack length (TCL) of microfissures first decreases with homogenization temperature and then increases, with a minimum occurring in the specimen heat treated at 1163 °. This trend coincides with the variation in segregation of B at grain boundaries with homogenization temperature and has been explained by equilibrium and nonequilibrium segregation of B to grain boundaries during the homogenization heat treatment. No other element was observed to segregate at the grain boundaries. The variation in volume fraction of phases like δ-Ni₃Nb, MC carbide, and Laves phases does not follow the same trend as that observed for TCL and B segregation at the grain boundaries. Therefore, microfissuring in HAZ of welded cast INCONEL 718 is attributed to the segregation of B at the grain boundaries.     

Nb的非平衡晶界偏聚动力学模拟与实验研究

摘要：Nb是现代高性能钢铁材料中重要的微合金化元素,其在晶界有强偏聚特性。采用3种Nb 空位复合体扩散系数分别对非平衡晶界偏聚进行拟合,根据铁 铌二元合金中Nb在晶界偏聚实验的EPMA测量结果筛选出最终的复合体扩散系数,并据此讨论了低温恒温温度,基体Nb含量,原奥氏体晶粒尺寸对非平衡晶界偏聚动力学的影响,得出了最符合实验结果的铌 空位复合体扩散系数公式。结果表明,在1000℃恒温过程,Nb非平衡晶界偏聚的临界时间在15min左右,临界时间常数为6.57×105。从1200℃固溶态冷却至某低温等温时,随着等温温度的升高临界时间迅速减小,Nb在晶界的最大偏聚量逐渐越小;随着基体Nb含量增加晶界Nb的最大偏聚量线性增加;随着原奥晶粒尺寸的增加临界时间逐渐增大。     

Cooling Rate Dependence of Boron Distribution in Low Carbon Steel

The behavior of boron (B) segregation to austenite grain boundaries in low carbon steel was studied using particle tracking autoradiography (PTA) and secondary ion mass spectroscopy (SIMS). An effective time method was used to compare the cooling rate (CR) dependence of this segregation during continuous cooling and its time dependence during isothermal holding. Comparison of these segregation behaviors has confirmed that the CR dependence of B segregation agrees well with its time dependence and is mainly a result of the phenomenon of nonequilibrium segregation. Based on the CR dependence of B segregation, the continuous cooling transformation behavior of B-bearing steel as compared with B-free steel was also investigated using dilatometry and microstructural observations. The addition of a small amount of B to low carbon steel retarded significantly the austenite-to-ferrite transformation and finally expanded the range of cooling programs that result in the formation of bainitic microstructures. Analysis of the B distribution has confirmed that this retardation effect of B on ferrite transformation is attributed to the CR dependence of B segregation to austenite grain boundaries during cooling after austenitization.     

Nonequilibrium solute segregation to austenite grain boundaries in low alloy ferritic and austenitic steels

Nonequilibrium segregations of substitutional solute and impurity elements to austenite grain boundaries during cooling from the austenitizing temperature have been measured in thin foil specimens of ferritic 2.25 pct Cr 1 pct Mo, 2.25 pct Cr 1 pct Mo 0.08 pct Sn and austenitic Type 316 steels using scanning transmission electron microscopy combined with energy dispersive X-ray spectrometry (STEM-EDS). The results are discussed and compared with the predictions of a theoretical analysis which describes the segregation in terms of a quench-induced diffusion of vacancy-solute atom pairs to the grain boundaries.     

Nonequilibrium solute segregation to austenite grain

Nonequilibrium segregations of substitutional solute and impurity elements to austenite grain boundaries during cooling from the austenitizing temperature have been measured in thin foil specimens of ferritic 2.25 pct Cr 1 pct Mo, 2.25 pct Cr 1 pct Mo 0.08 pct Sn and austenitic Type 316 steels using scanning transmission electron microscopy combined with energy dispersive X-ray spectrometry (STEM-EDS). The results are discussed and compared with the predictions of a theoretical analysis which describes the segregation in terms of a quench-induced diffusion of vacancy-solute atom pairs to the grain boundaries.     

Correlation Between MnS Precipitation,Sulfur Segregation Kinetics,and Hot Ductility in C-Mn Steel

In a C-Mn steel without Nb, the mechanism of hot ductility loss and recovery has been understood. The specimens were solution treated at 1673 K (1400 °C), subsequently cooled to 1273 K (1000 °C) at a rate of 1 or 20 K/s and finally held at the temperature. At a rate of 1 K/s, the segregation concentration of sulfur at prior austenite grain boundaries decreases gradually with holding time. At the rate of 20 K/s, the segregation concentration of sulfur shows a convex profile in a time versus segregation concentration plot. Such segregation behaviors of sulfur are deeply related to the MnS reaction during cooling to 1273 K (1000 °C) or holding at the temperature. The high-temperature intergranular fracture observed in this steel is due to the sulfur segregated at the grain boundaries. The recovery of hot ductility results from the combination between the decrease in sulfur segregation concentration governed by the MnS reaction and the overall decohesion at the interface of the MnS particles which act as a strong sink of the free sulfur tending to segregate to the grain boundaries.     

Surface and grain boundary segregation of deuterium in nickel

The segregation of deuterium to surfaces and grain boundaries in nickel has been studied using SIMS (secondary ion mass spectroscopy) techniques. Conditions for optimizing the detection of deuterium are discussed. Segregation of deuterium to external surfaces and grain boundaries was shown to occur at temperatures near 300 K The segregation of sulfur to the external surfaces was also studied and co-segregation effects for sulfur and deuterium were examined. In the presence of sulfur, segregation of deuterium to surfaces was shown to occur at temperatures as high as 845 K.     

The grain boundary segregation of boron during isothermal holding

Boron segregation to grain boundaries was investigated by means of particle tracking autoradiography (PTA) in a low carbon and two Mo-bearing steels and in an Fe-30% Ni alloy. Non-equilibrium segregation took place after rapid cooling to a degree which increased as the temperature difference between the austenitization and subsequent holding temperatures was increased. The amount of deformation during isothermal holding had a similar effect. The maximum segregation produced in this way can be many times higher than that associated with equilibrium segregation. The observations support the view that boron atoms are transported to the boundaries by forming complexes with vacancies which migrate to the boundaries prior to annihilation. During holding at different temperatures, the boron intensity curves produced by the PTA method exhibit three types of time dependence. Two of these involve the appearance of a segregation peak, after which there is either complete or partial disappearance of the segregation. The former is associated with the back diffusion of boron into the depleted zone, a process that takes place at the highest holding temperatures and in the absence of precipitation. The latter involves the conversion of temporary segregation into grain boundary precipitates and is observed at intermediate temperatures. The third type is observed at the lowest temperatures; in this case the development of non-equilibrium segregation is converted into precipitation prior to the appearance of segregation peak. The temperature range associated with each type of curve depends on the relation between the kinetics of non-equilibrium segregation on the one hand and that of precipitation on the other.     

Grain boundary damping in substitutional alloys

A study was made of the grain boundary damping characteristics of twelve Cu?Ni alloys, chosen to cover the entire range of solid solutions. The height, temperature, and activation energy of the solute peak was used to investigate solute segregation to grain boundaries. A criterion was developed to determine solute build up in the grain boundaries, and when applied to other alloy systems, it verified the well known equilibrium segregation concept due to Mclean.¹² The qualitative model for the low temperature peak in fcc pure metals¹⁰ was modified to incorporate segregation effects and thus explain the origin of the solute peak in dilute alloys. The model explained, without modification, the behavior of a concentrated alloy, as long as it was a complete solid solution.     

Effect of Annealing and Hot Rolling on Grain Boundary Segregation of Arsenic in an Mn-Steel Microalloyed by Ti,Cr and Nb

Steel samples with size of 10 mm×10 mm×5 mm were cut down from a hot-rolled Mn-steel microalloyed by Ti, Cr and Nb and produced by compact strip production (CSP) technology. The samples were annealed at 950 °C for different time firstly, and then hot rolled or cooled in the air, in water and in furnace, respectively. Auger electron spectroscopy (AES) was used to study the effects of annealing and hot rolling on the segregation of arsenic at grain boundary (GB) in the steel. The results indicated that a higher content of arsenic was found at grain boundaries than in the matrix when the steel was annealed at 950 °C for 2 h and then cooled to room temperature by water quenching. But the content of arsenic at grain boundaries was similar to that in the matrix when the steel was annealed at 950 °C for 2 h and then cooled to room temperature by furnace cooling. A longer holding time, such as 12 h and 36 h at 950 °C, resulted in a similar arsenic content at grain boundaries to that in the matrix of the steels. Hot rolling led to a similar content of arsenic at grain boundaries and within grains in the steels as well.     

Grain boundary segregation of antimony in iron base alloys and its effect on toughness

The equilibrium grain boundary segregation of antimony was investigated in iron base alloys (Fe-Sb, Fe-C-Sb, Fe-Ni-Sb) after annealing at temperatures between 550 and 750°C. Utilizing Auger electron spectroscopy (AES) the concentration of antimony at intergranular fracture faces was determined as a function of bulk concentration and equilibration temperature. The segregation of antimony in Fe-Sb alloys with mass contents of between 0.012 and 0.094 % Sb was described by the Langmuir-McLean equation. The evaluation leads to the free enthalpy of segregation ΔG_segr = ?19 kJ/mol - T 28 J/mol K. The relatively low value for the segregation enthalpy ΔH = ?19 kJ/mol indicates a rather small tendency for grain boundary segregation of Sb. However, its embrittling effect is strong, scanning electron micrographs (SEM) of fractured samples show that the percentage of intergranular fracture strongly increases with an increasing coverage of antimony at the grain boundaries. The data for Fe-0.93% Sb and Fe.1.91% Sb (mass contents) do not fit in the thermodynamic evaluation obviously due to formation of antimonide precipitates in the grain boundaries. The addition of carbon to Fe-Sb alloys results in a higher grain boundary cohesion which is caused by two effects of carbon, displacement of antimony from the grain boundaries by carbon and enhanced grain boundary cohesion. In the Fe-Ni-Sb alloys additional segregation of nickel was found at the grain boundaries but no enhanced antimony segregation, as expected from previous models of other authors, assuming Ni-Sb cosegregation.     

High temperature brittle intergranular cracking in high strength nickel alloys undoped and doped with S,Zr, and/or B—II. Solute segregation analysis

In order to clarify the mechanism of high temperature brittle intergranular cracking in high strength nickel alloys, solute segregation at grain boundaries and on high temperature fracture surfaces has been examined by scanning Auger microscopy. Intergranular S segregation producing global embrittling effects was found to increase in the following order: alloys with low S or high S and Zr, high S and B, and high S. The grain boundaries extensively contained Ti or Zr rich sulfides in the S-doped alloys and B segregation inducing intergranular toughening in the alloy with high S and B. The alloys with low S, and high S and B showed more strongly S segregation on high temperature fracture surfaces, which was much greater compared with at grain boundaries, than with high S, and high S and Zr. The local stress intensification did not produce a remarkable S enrichment at grain boundaries except near sulfides. It is proposed that S fluxes from crack surfaces and stressed sulfides to the crack tip induce local embrittlement. The composition and temperature effects on the brittle cracking behavior are discussed in terms of the global and local embrittling effects.     

Effect of Trace Levels of Si on Microstructure and Grain Boundary Segregation in DOP-26 Iridium Alloy

The thermodynamics and kinetics of Silicon (Si) segregation to grain boundaries in Iridium alloy DOP-26 with added trace levels of Si of 6, 11, 29, and 36 wppm was studied by Auger Electron Spectroscopy. The four alloys were annealed at 1500 or 1535 °C for 19 or 76 hours followed by cooling at three different rates. Si enrichment at the grain boundaries (GB) increased with increasing bulk Si content, with the grain boundary Si enrichment factors ranging from 62 to 344, depending on the bulk Si content and the cooling rate. Grain boundary Si contents increased with decreasing cooling rate in all alloys, indicating that Si GB segregation is influenced by both thermodynamic and kinetic factors in the alloys and temperature ranges of the study. A Langmuir-McLean isotherm-based model was successfully used to predict the temperature dependence of GB Si segregation in DOP-26 alloys with Si additions and estimate the temperature independent free energy of Si segregation to grain boundaries in DOP-26.     

含磷高强IF钢拉矫断带的原因及机制

 采用场发射SEM及TEM研究了含磷高强IF钢拉矫断带的断口形貌及析出物的分布状态,结果表明导致断带的主要原因是晶界处大尺寸、树枝状Fe(Nb,Ti)P相的偏聚析出。通过对断带样品的热处理回溶试验及不同层冷冷速的热模拟试验,分析了造成Fe(Nb,Ti)P相晶界富集析出的温度范围及工艺要素。在机制研究的基础上,制定了热轧生产的控制要点,主要包括轧制温度、层冷冷速、成分设计、卷取温度等多个方面,成功抑制了高P类高强IF钢的拉矫断带事故发生率。     

Grain boundary segregation of boron in INCONEL 718

The segregation behavior of boron at grain boundaries in two INCONEL 718⁺ based alloys with different B concentrations was studied. The alloys, one containing 11 ppm of B and the other 43 ppm, were homogenized at 1200 °C for 2 hours followed by water quenching and air cooling. A strong segregation of boron at grain boundaries was observed using secondary ion mass spectrometry after the heat treatment in both the alloys. The segregation was found mainly to be of nonequilibrium type. The homogenized samples were also annealed at 1050 °C for various lengths of time. During annealing, boride particles were observed to first form at grain boundaries and then to dissolve on continued annealing at 1050 °C. The mechanisms of segregation and desegregation of B are discussed.     

Role of grain boundary segregation in diffusional creep

The high temperature deformation of polycrystalline materials by the stress directed flow of vacancies is now a well established creep mechanism which operates in two temperature regimes: high temperature, or Nabarro-Herring creep, in which lattice diffusion is rate determining, and low temperature, or Coble creep, in which grain boundary diffusion predominates. Basic studies have been conducted mostly with pure metals for which there exists in general a good correspondence between predicted and observed behavior. Multicomponent engineering alloys will normally experience, as part of their processing history or service lives, the segregation enrichment of interfaces such as grain boundaries by species present in solid solution. The aim of this paper is to evaluate the experimental information and to explore the manner in which this segregation affects the principal forms of diffusional creep. Cases of retarded Herring-Nabarro creep are analyzed in terms of the efficacy of grain boundaries as sources and sinks for vacancies: strongly bound segregant atoms at grain boundaries affect the mobility of defects and hence control the operation of vacancy sources. Recently, observations have been made on the effect of strongly segregating solutes on grain boundary diffusivity. Such behavior influences Coble creep rates, producing in general a retardation. Here we assess the magnitude of the effect induced by various surface active species on grain boundary diffusivity and consequently on Coble creep; predictions show that in general, small amounts of highly surface active impurities induce a remarkable inhibition of this form of creep.     

High temperature ductility loss in carbon-manganese and niobium-treated steels

The causes of embrittlement in several plain carbon-manganese and niobium-treated steels between 800 and 1200 °C have been investigated. Tensile ductility was measured as a function of temperature and strain rate. Percent elongation and reduction in area were used to characterize the temperature dependence and severity of the ductility loss. The size, distribution, and composition of grain boundary precipitates were measured on extraction replicas. Grain boundary segregation was measured by AES on samples that were deformed at 900 °C before being fractured under ultra-high vacuum at room temperature. Segregation of impurity residual elements and grain boundary precipitation are the primary factors responsible for the observed ductility loss. The embrittlement results in a low ductility fracture which is largely intergranular through the austenite grain boundaries. Segregation of Cu, Sn, and Sb was found on the fracture surfaces of the embrittled samples. High temperature deformation was necessary to produce segregation as no segregation was detected in undeformed samples. Grain boundary precipitation, particularly AIN but also Nb (C,N), contributed to the embrittlement when there was a relatively fine distribution of precipitates along the austenite grain boundaries. The most severe ductility loss occurred when grain boundary precipitation combined with Cu, Sn, and Sb segregation. Formerly Graduate Student, Lehigh University     

The effect of trace element additions on the grain boundary composition of Ir + 0.3 pct W alloys

The grain boundary fracture surfaces of several Ir + 0.3 pct W alloys have been examined using Auger electron spectroscopy. Dopant additions (between 10 and 80 wt ppm) of Al, Fe, Th, Ni and Rh are shown to result in thorium enriched grain boundaries. Inert ion sputtering experiments suggest that the thorium enriched region at the grain boundaries is probably only a few atom layers thick. The other dopants (Al, Fe, Ni and Rh) do not appear to influence the segregation of thorium, and their function (if any) in improving the high temperature impact properties of this alloy is unclear at this time.