Oxidation behavior of 4774DD1 Ni-based single-crystal superalloy at 980℃ in air

The oxidation behavior of a novel Ni-based single-crystal 4774DD1 superalloy for industrial gas turbine applications was investigated by the isothermal oxidation at 980℃ and discontinuous oxidation weight gain methods.The phase constitution and morphology of surface oxides and the characteristics of the crosssection oxide film were analyzed by XRD,SEM and EDS.Results show that the oxidation kinetics of the 4774DD1 superalloy follows the cubic law,indicating its weak oxidation resistance at this temperature.As the oxidation time increases,the composition of the oxide film evolves as following:One layer consisting of a bottom Al_(2)O_(3)sublayer and an upper(Al_(2)O_(3)+NiO)mixture sublayer after oxidized for 25 h.Then,two layers composed of an outermost small NiO discontinuous grain layer and an internal layer for 75 h.This internal layer is consisted of the bottom Al_(2)O_(3)sublayer,an intermediate narrow CrTaO_(4)sublayer,and an upper(Al_(2)O_(3)+NiO)mixture sublayer.Also two layers comprising an outermost relative continuous NiO layer with large grain size and an internal layer as the oxidation time increases to 125 h.This internal layer is composed of the upper(Al_(2)O_(3)+NiO)mixture sublayer,an intermediate continuous(CrTaO_(4)+NiWO_(4))mixture sublayer,and a bottom Al_(2)O_(3)sublayer.Finally,three layers consisting of an outermost(NiAl2O_(4)+NiCr2O_(4))mixture layer,an intermediate(CrTaO_(4)+NiWO_(4))mixture layer,and a bottom Al_(2)O_(3)layer for 200 h.

Evolution mechanism of crystallographic orientation in grain continuator bars of a Ni-based single-crystal superalloy prepared by Bridgman technology during directional solidification

Single-crystal rods with different diameters and deviation angles with respect to the solidification direction were produced by Bridgman rapid solidification method at withdrawal rates of 3 and 6 mm·min^(-1) and used as grain continuators.The crystallographic orientation of the rods,which cross-sections were perpendicular to the solidification direction at different solidification heights,was measured by electron backscattered diffraction,while the corresponding microstructures were observed by optical microscopy.The mushy zone morphology and the distribution of the temperature gradient were simulated by the finite element analysis software ProCAST.The experimental results indicate that the crystallographic orientation of the single-crystal rods corresponds to the statistical average value of all the dendrite orientations in cross-section.The crystallographic orientation of the primary and secondary dendrites of each single-crystal rod at different cross-sections fluctuates irregularly within a small range(less than 4°).The crystallographic orientation of the dendrite in each single-crystal rod is not exactly consistent with each other and is affected by their branching mode of dendrites in the solidification space.In addition,the simulation results show that the mushy zone shapes and the temperature gradient of single-crystal rods change with the increase of solidification height during the solidification process.Finally,the evolution mechanism of the crystallographic orientations and the corresponding influence factors were analyzed and discussed.

Molecular dynamics study of mosaic structure in the Ni-based single-crystal superalloy

The mosaic structure in a Ni-based single-crystal superalloy is simulated by molecular dynamics using a potential employed in a modified analytic embedded atom method. From the calculated results we find that a closed threedimensional misfit dislocation network, with index of （011）{100} and the side length of the mesh 89.6A, is formed around a cuboidal γ′ precipitate. Comparing the simulation results of the different mosaic models, we find that the side length of the mesh only depends on the lattice parameters of the γ and γ′ phases as well as the γ/γ′ interface direction, but is independent of the size and number of the cuboidal γ′ precipitate. The density of dislocations is inversely proportional to the size of the cuboidal γ′ precipitate, i.e. the amount of the dislocation is proportional to the total area of the γ/γ′ interface, which may be used to explain the relation between the amount of the fine γ′ particles and the creep rupture life of the superalloy. In addition, the closed three-dimensional networks assembled with the misfit dislocations can play a significant role in improving the mechanical properties of superalloys.

The ternary Ni–Al–Co embedded-atom-method potential for γ/γ Ni-based single-crystal superalloys: Construction and application

An Ni-AI-Co system embedded-atom-method potential is constructed for the γ（Ni）/γ＇（Ni3A1） superalloy based on experiments and first-principles calculations. The stacking fault energies （SFEs） of the Ni（Co, A1） random solid solutions are calculated as a function of the concentrations of Co and A1. The calculated SFEs decrease with increasing concentrations of Co and A1, which is consistent with the experimental results. The embedding energy term in the present potential has an important influence on the SFEs of the random solid solutions. The cross-slip processes of a screw dislocation in homogenous Ni（Co） solid solutions are simulated using the present potential and the nudged elastic band method. The cross-slip activation energies increase with increasing Co concentration, which implies that the creep resistance of γ（Ni） may be improved by the addition of Co.

Growth of Casting Microcrack and Micropore in Single-crystal Superalloys Analysed by Three-Dimensional Unit Cell

Finite element （FE） analysis was employed to investigate the casting microcrack and micropore growth in nickel-base single-crystal superalloys DD3. Based on the finite deformation rate-dependent crystallographic constitutive equation, the simulations of casting microcrack and micropore growth in three-dimensional unit cell model were carried out in a range of parameters including stress triaxiality, Lode parameter and type of activated slip systems. The FE results show that the stress triaxiality has profound effects on growth behavior, and the Lode parameter is also important for the casting microcrack and micropore growth. The type of operative slip systems has remarkable effect on casting microcrack and micropore growth, so the life of single- crystal component is associated with the type of activated slip systems, which is related to Schmid factor and the number of activated slip systems. The growth comparison between microcrack and micropore reveals that when the material is subjected to large deformation, the growth rate of microcrack is faster than that of micropore, i.e. microcrack is more dangerous than micropore; the microcrack is easier to result in brittle fracture than micropore. The stress triaxiality and Lode parameter have strong influence on the growth of microcrack and micropore.

Solidification Microstructures of a Single-crystal Superalloy under Ultra-high Temperature Gradient Conditions

The solidification microstructures and solute segregation of a newly developed hot corrosion resistant single-crystal Ni-base superalloy were investigated with a zone-melting and ultra-high thermal gradient unidirectional solidification apparatus.Compared with the microstructures solidified at conventional low thermal gradient conditions,the dendrite arm spacings,the interdendritic microporosity and γ/γ' eutectic,and the severity of solute segregation of the single-crystal superalloy solidified at ultra-high thermal gradient conditions were considerably reduced.It was shown that the microstructure solidified under ultra-high thermal gradient condition is ideal for the full exploitation of the excellent property potentials of single-crystal superalloys.

Discontinuous Precipitation Reaction Front of Cellular Recrystallization for a Single-Crystal Superalloy Studied by Electron Microscopy

Combining analytical transmission electron microscopy systematic tilting, scanning transmission electron microscopy mapping and nano-beam electron diffraction operations, we obtain direct experimental proofs on the boundary type, elemental distribution and structure of the cellular reerystallization reaction front for a single- crystal superalloy. It is demonstrated that the cellular recrystallization reaction front usually corresponds to coincidence site lattice boundaries, and a thin layer of γ-forming elements such as Re, Cr, Mo and Co invariably exists in the direct reaction front. Furthermore, the thin layer with γ-forming elements is proved to be γ phase, with the same orientation as the neighboring original matrix.

Effect of surface recrystallization on the creep rupture property of a single-crystal superalloy

The effect of surface recrystallization by heating after shot-peening on the creep rapture property and fracture behavior of a single-crystal superalloy was investigated. The results show that the creep rupture property of the single-crystal superalloy was greatly influenced by surface recrystallization. A recrystallized surface layer with a depth of 101 ~m resulted in a decrease in creep rupture life by nearly 50%, and an almost linear reduction of creep rupture life was observed with the increase of recrystallization depth. A lower strength of the recrystal- lized layer, inhomogeneous deformation between the recrystallized layer and the matrix, and stress concentration caused by notch effect resuited in the decrease in creep rupture life of the single-crystal superalloy.

Recrystallization of SRR99 single-crystal superalloy: Kinetics and microstructural evolution

As-cast SRR99 specimens were shot-peened and then annealed at 1250 and 1300°C for different times to investigate the kinetics of recrystallization.It was found that the relationship between annealing time and volume fraction of recrystallized grains could be described by the Johnson-Mehl-Avrami equation.Based on the kinetics analysis of the recrystallization process,the apparent activation energy for recrystallization was determined.In addition,the microstructural evolution during the recrystallization process at 1300°C was studied.Inwards,recrystallization first occurs in the dendritic core regions at the shot-peened surface.With the dissolution of coarse γ＇ particles in the interdendritic regions,the recrystallized grain boundaries move through the interdendritic regions.Finally,the fully developed grains nearly have a uniform depth.The recrystallization process at the shot-peened surface is similar to that of wrought materials,which includes nucleation of recrystallization,growth of recrystallized nuclei into the matrix,and growth of recrystallized grains by swallowing up each other.

Effect of H impurity on misfit dislocation in Ni-based single-crystal superalloy:molecular dynamic simulations

The effect of H impurity on the misfit dislocation in Ni-based single-crystal superalloy is investigated using the molecular dynamic simulation. It includes the site preferences of H impurity in single crystals Ni and Ni3Al, the interaction between H impurity and the misfit dislocation and the effect of H impurity on the moving misfit dislocation. The calculated energies and simulation results show that the misfit dislocation attracts H impurity which is located at the γ/γ′ interface and Ni3Al and H impurity on the glide plane can obstruct the glide of misfit dislocation, which is beneficial to improving the mechanical properties of Ni based superalloys.

Effect of Magnetic Field Configuration on Stray-Crystal Formation with Different Platform Sizes during Directional Solidification of Single-Crystal Superalloy

The magnetic field is an effective means to control the solidification structure and the defects of metal and semiconductor crystals.This work investigates the effects of Cusp magnetic field(CMF)and longitudinal magnetic field(LMF)on the stray-crystal formation in the platform regions during the directional solidification of single-crystal superalloy with the different cross section sizes.The application of CMF reduces the formation of platform stray-crystal,while LMF increases its generation.As the platform size increases,the stray-crystal ratio increases regardless of whether the magnetic fields are applied or not,the effectiveness of CMF increases,while that of LMF decreases.The reason that the effects of CMF and LMF on the platform stray-crystal formation could be attributed to the change of flow structure from the distribution characteristics of the thermoelectric magnetic force and the magnetic damping force near the liquid-solid interface.

Possibility and stabilizing effect of Mo clusters in the Ni-based single-crystal superalloy

Nickel-based single-crystal superalloys are crucial materials for the preparation of aero-engine turbine blades. Many solute elements are added to superalloys for strengthening. However, the relationship between the clustering behavior of solute atoms and the properties of nickel-based single-crystal superalloys is still unclear. Herein, we conduct first-principles calculations onγ phases with Mo-Mo and Mo-Mo-Ru clusters to reveal the possibility and stabilizing mechanism of solute clusters. Introducing Mo lowers the total energy, binding energy, and formation energy of the γ phase due to the replacement of weak Ni-Ni interaction with strong Mo-Ni bonding. Note that the γ phase containing the Mo-Mo cluster is more stable than that containing a Mo single atom, possibly owing to a wide affecting range. The Ru atom added to the γ phase can further boost system stability, and it tends to form a Mo-Mo-Ru cluster. The stabilizing impact of the Mo-Mo-Ru cluster is demonstrated to be the replacement of weak Ni-Mo interaction by the strong Ru-Mo interaction, which may be derived from the enhanced d-orbital hybridization.

Microstructure and creep properties of Ni-based single-crystal superalloys with Mo/Al addition at 760℃/850 MPa

The effect of Mo and Al addition on the microstructure as well as creep rupture properties at760.C/850 MPa was investigated by transmission electron microscopy(TEM)in a Ni-based single-crystal(SC)alloy with the composition of Ni-6.5Al-8.0Mo-2.4Cr-6.2Ta-4.9Co-1.5Re-(0.01-0.05)Y(wt%).The microstructure analysis shows that 0.5 wt%Al addition induces rapid decrease in creep rupture life,and this can be attributed to the formation of dense stacking faults cutting intoγ'precipitates,which can be explained by the increase in Orowan stress caused by the narrowerγchannel width and the decrease in stacking faults energy.Besides,1.5 wt%Mo addition increases the anti-phase boundary energy and decreases the stacking faults energy,resulting in fewer stacking faults and thus a slight decrease in the creep rupture life.

In-situ coating and surface partial protonation co-promoting performance of single-crystal nickel-rich cathode in all-solid-state batteries

The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.

Insight into the capacity degradation and structural evolution of single-crystal Ni-rich cathodes

Single-crystal Ni-rich cathodes are a promising candidate for high-energy lithium-ion batteries due to their higher structural and cycling stability than polycrystalline materials.However,the phase evolution and capacity degradation of these single-crystal cathodes during continuous lithation/delithation cycling remains unclear.Understanding the mapping relationship between the macroscopic electrochemical properties and the material physicochemical properties is crucial.Here,we investigate the correlation between the physical-chemical characteristics,phase transition,and capacity decay using capacity differential curve feature identification and in-situ X-ray spectroscopic imaging.We systematically clarify the dominant mechanism of phase evolution in aging cycling.Appropriately high cut-off voltages can mitigate the slow kinetic and electrochemical properties of single-crystal cathodes.We also find that second-order differential capacity discharge characteristic curves can be used to identify the crystal structure disorder of Ni-rich cathodes.These findings constitute a step forward in elucidating the correlation between the electrochemical extrinsic properties and the physicochemical intrinsic properties and provide new perspectives for failure analysis of layered electrode materials.

Understanding the failure mechanism towards developing high-voltage single-crystal Ni-rich Co-free cathodes

Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.

Dynamic recrystallization of single-crystal nickel-based superalloy

The dynamic recrystallization behavior of single-crystal（SC） superalloy SR.R99 at low strain rate was investigated by high-temperature creep testing.The results show that dynamic recrystallization may take place after the uncoated samples have been creep-tested in air at high temperature and low stress for a long time.Both the threshold temperature and strain for the dynamic recrystallization of SC superalloy SRR99 at low strain rate are lower than those for the static recrystallization.Dynamically recrystallized grains with the depth less than 15 μm are only located in the surface γ＇-free layers,and the recrystallized grains are well-developed grains without columnar y＇precipitates within them.The dynamic recrystallization behavior of SC superalloy SRR99 at low strain rate is mainly related to high-temperature oxidation.Suitable protective coating can effectively prevent the dynamic recrystallization of SC superalloy components in service.In addition,the dynamic recrystallization behavior of SC superalloy SRR99 at high strain rate was also studied by high-temperature compression testing.At high strain rate,a higher temperature and larger strain are needed for the occurrence of dynamic recrystallization than at low strain rate,and the recrystallized grains have cellular structures with an amount of columnar γ＇ precipitates within them.

Microstructure and composition evolution of a single-crystal superalloy caused by elements interdiffusion with an overlay NiCrAlY coating on oxidation

MCrAlY(M=Ni and/or Co)overlay coating is widely used as a protective coating against high temperature oxidation and corrosion.However,due to its big difference in chemical composition with the underlying superalloy,elements interdiffusion occurs inevitably.One of the direct results is the formation of interdiffusion zone(IDZ)and secondary reaction zone(SRZ)with a high density of fine topological closed-packed phases(TCPs),weakening dramatically the mechanical properties of the alloy substrate.It is by now the main problem of modern high-temperature metallic coatings,but there are still hardly any reports studying the formation,growth and transformation of IDZ and SRZ in deep,as well as the precipitation of TCPs.In this work,a typical NiCrAlY coating is deposited by arc ion plating on a single-crystal superalloy N5.Elements interdiffusion between them and its relationship on microstructure were clarified.Cr rather than Al from the coating diffuses into the alloy at high temperatures and segregates immediately beneath their interface,contributing largely to the formation of IDZ.Simultaneously,diffusion of Ni from the deep alloy to IDZ leads to the formation and continuous expansion of SRZ.

Isothermal oxidation behavior of a new Re-free nickel-based single-crystal superalloy at 950℃

The isothermal oxidation behavior of a new Refree nickel-based single-crystal superalloy in air at 950 ℃ for 200 h was studied by scanning electron microscopy（SEM）with energy-dispersive spectroscopy（EDS）and X-ray diffraction（XRD）.The results indicate that oxidation kinetics obeys parabolic law approximately,and the mass gain increases rapidly during initial oxidation stage and then gradually slows down.The oxidation scales are composed of three layers：the outer layer mainly consists of NiO with a small amount of CoO;the intermediate layer is mainly composed of Cr_2O_3 with a small amount of spinel compounds such as CrTaO_4,NiCr_2O_4,CoCrAl_2O_4,CoAl_2O_4,and NiAl_2O_4;and the inner layer is composed of Al_2O_3.Inner Al_2O_3 layer suppresses the diffusion of elements between oxygen and alloy elements,slows down the alloy oxidation speed,and also suppresses the growth of the oxide scale and reduces the oxidation rate,which is agreeable with the oxidation kinetics.

Creep prediction model for nickel-based single-crystal superalloys considering precipitation of TCP phase

The microstructure of nickel-based single-crystal(SC) superalloys has a pivotal influence on their creep properties. The addition of the Re element not only enhances the long-term creep properties of nickel-based SC superalloys, but also results in the formation of a topologically close-packed(TCP) phase which is a harmful and brittle hard phase. Here, high-temperature creep interruption tests of a nickel-based SC superalloy that contains4.8 wt% Re were performed under various temperatures and stress conditions, and the evolution of microstructure during creep was observed by scanning electron microscopy(SEM). The volume fraction of the TCP phase was also extracted to explore the mechanism that controls the impacts of the TCP phase on the creep properties.According to the microstructure evolution mechanism, the influence of the TCP phase was attributed to the initial damage and critical shear stress of the material. A creep performance prediction model for nickel-based SC superalloys considering the precipitation of the TCP phase that is based on the crystal plasticity theory and a modified creep damage model was established. The simulation curves fit well with the experimental results and the errors between prediction creep life with test results are within 5%.