Theoretical progress in non-equilibrium grain-boundary segregation (Ⅰ): Thermally induced non-equilibrium grain-boundary segregation and intergranular embrittlement

The research progress of non-equilibrium grain-boundary segregation theories in the last 20 years is reviewed. Based on studies by the present authors, the critical time of non-equilibrium segregation and its impact on the development of non-equilibrium segregation theories are described. Quasi- thermo- dynamics and kinetics for thermal non-equilibrium grain boundary segregation are detailed along with a non-equilibrium grain boundary cosegregation model. The experimental validation of the theories and their application to the reversible temper embrittlement of steels and the intermediate temperature brittleness in metals and alloys are also addressed.

Non-equilibrium Grain-boundary Segregation of Phosphorus in an Fe-17Cr Alloy

In order to confirm the segregation characteristic of phosphorus in an Fe-17Cr alloy at grain boundary, the phosphorus segregation was obtained by Auger electron spectroscopy. The results show that a maximum phosphorus segregation appeared at 450 ℃ for all specimens aged for 30 rain at 350, 400, 450, 500, and 600 ℃ after being solution-treated at 1 000 ℃ for 1 h. These results were analyzed by the characteristics of segregation peak temperature of non-equilibrium segregation.

NON-EQUILIBRIUM SOLUTE SEGREGATION TO AUSTENITIC GRAIN BOUNDARY IN FERRUM-NICKLE ALLOY

The development of non-equilibrium segregation of boron at grain boundaries in Fe-4 0%Ni alloy during continuous cooling process was experimentally observed with boron Particle Tracking Autoradiography (PTA) and Transmission Electron Microscopy (TEM,). The samples with 10ppm boron were cooled at 2℃/s to 1040, 980, 920, 860, 780 and 640℃ respectively after pre-heat treatment of 1150℃ for 15mm with a Gleeble-1500 heat simulating machine, then water quenched to room temperature. The width of segregation layer and boron depletion zone, rich factor and other parameters were measured by a special image analysis system. The experimental results of PTA show that the grain boundary segregation of boron during cooling process is a dynamic process and the development of the non-equilibrium segregation experiences three stages: first increases rapidly from 1150 to 1040℃, then gently from 1040 to 860℃, and rapidly again from 860℃ to 640℃. The width of boron depletion zone increases from about 11μm at 1040℃ to 26μm at 640℃. TEM observation shows that boron precipitates exist at grain boundaries when the samples are cooled to below 860℃. The experimental phenomena are briefly discussed.

The Role of Nd Solid-Solution and Grain-Boundary Segregation in Binary NiAl Intermetallic Compound

The role of Nd solid-solution and grain-boundary segregation in binary NiAl alloy was studied based on microhardness and compressive macrostrain. X-ray and Auger spectra studies indicate that Nd not only is soluble in grain interiors, but also segregates to the grain boundaries. Nd solid-solution induces an increase of the microhardness from 269 to 290 HV in grain interiors and segregation results in an enhancement of hardness from 252 to 342 HV on grain boundaries. Thus, the cohesion of grain boundaries is enhanced by Nd segregation, which make the alloy doped with 0.05 wt pct Nd exhibit more compressive microstrain, i.e. the higher the compressive ductility at room temperature, the better the final surface condition at elevated temperature. Finally, a discussion was made on the reason that Nd strengthens the grain boundaries in NiAl intermetallic alloy.

NON-EQUILIBRIUM SEGREGATION OF Si ON Al-0.35 wt-% Si ALLOY SURFACE

Si segregation was observed in the vacancy condensation pits,formed by supersaturated vacancies beneath the oxidation layer of Al-0.35wt-％Si alloy,by optical microscopy,X- ray photoelectron spectroscopy and microhardness tests.This phenomenon could only be explained by vacancy-Si complex inducing non-equilibrium segregation.

NON-EQUILIBRIUM SEGREGATION OF SOLUTE TO GRAIN BOUNDARIES

In consideration of the local equilibrium among vacancies,solute atoms and vacancy-solute atom complexes and the influence of equilibrium grain boundary segregation,theoretical dy- namic formulas for non-equilibrium grain boundary segregation of solute have been derived on the basis of the vacancy-dragging mechanism.Theoretical calculation by computer has been carried out for the non-equilibrium segregation of boron to austenitic grain boundaries during isothermal holding and continuous cooling after heating at high temperatures.The re- suits agree well with those obtained from experiments.

Dynamic process of trace boron non-equilibrium grain boundary segregation and the effect of cooling rate

The dynamic process of non-equilibrium grain boundary segregation of traceboron in Fe-40 percent Ni alloy during cooling and the effect of cooling rate were investigated byboron tracking autoradiography technique. The results indicate that during cooling process, theamount of segregated boron on grain boundary firstly increases fast, then enters a comparativelyeven increasing stage and increases rapidly again at the third stage. The details of each stagevaried with cooling rate are explained. When the segregation develops to a certain degree, thesegregated boron atoms transform from solute status to precipitate status.

Creating and destroying vacancies in solids and nonequilibrium grain boundary segregation

How the vacancies in excess of equilibrium concentration are created and destroyed in solids is crucial for understanding many of their physical characteristics and processes. Grain boundaries are known as sources and sinks for bulk vacancies, but what exchange will occur between the grain boundary and the bulk under a stress is still obscure. In the present paper, we show that grain boundaries will work as sources to emit vacancies when a compressive stress is exerted on them and as sinks to absorb vacancies when a tensile stress is exerted. This is the sixth method of introducing and annihilating vacancies in solids in addition to the five methods mentioned in literature. At the same time, this physical process will produce solute nonequilibrium grain-boundary segregation/dilution. A set of kinetic equations is established to describe such a physical process. Additionally an attempt has been made to simulate Misra抯 experimental data with the kinetic equations to justify the physical process.

INFLUENCE OF TIN ON THE HOT DUCTILITY OF A LOW-CARBON STEEL

The influence of tin on the hot ductility of a 0.15wt%C steel is investigated using a continuous-casting thermal simulator with three cooling rates. Tin can apparently deteriorate the hot ductility of the steel. Non-equilibrium grain boundary segregation of tin occurs during cooling and plays an important role in reducing the hot ductility of the steel. There is a critical cooling rate for the Sn segregation being between 5 and 20K/s.

MECHANISM FOR DIFFUSION OF BORON IN γ-Fe

Mechanism for diffusion of B in γ-Fe is believed to be mainly by means of boron-vacancy complexes other than as interstitial atoms previously.This was made of calculation on the ba- sis of theoretical model proposed by the authors.The calculated diffusion coefficient of B in γ-Fe after this mechanism is consistent with the experimental values.In addition,this is also supported by the non-equilibrium segregation phenomenon of B at grain boundaries of γ-Fe and the lattice constant measurement of Fe-B alloy.

Effect of rare earth cerium on brittleness of simulated welding heat-affected zones in a reactor pressure vessel steel

The welding coarse-grained heat-affected zones（CGHAZs） in the undoped and Ce-doped samples of SA508CL-3 reactor pressure vessel steel were simulated using a Gleeble 1500 D thermomechanical simulator with a peak temperature of 1320 oC at the heat inputs of 30, 50 and 100 kJ /cm, respectively. The ductile-to-brittle transition temperature（DBTT） of the simulated CGHAZs was evaluated along with microstructural and microchemical characterizations. The results indicated that Ce could substantially lower the DBTT of the CGHAZs by its microstructural and microchemical effects. After the thermal cycling of welding, the microstructure in the Ce-doped samples was apparently finer than that in the undoped samples, regardless of the lath bainite obtained at the heat inputs of 30 and 50 kJ /cm or the granular bainite acquired at the heat input of 100 kJ /cm, leading to lower DBTTs for the Ce-doped samples. Moreover, grain boundary segregation of Ce occurred apparently in the Ce-doped samples and exhibited a non-equilibrium characteristic. The segregation of Ce could play an important role in lowering the DBTT of CGHAZs or toughening the CGHAZs.