Synthesis and oxidation behavior of platinum-enriched γ + γ′ bond coatings on Ni-based superalloys

Simple Pt-enriched γ + γ′ coatings were synthesized on René 142 and René N5 Ni-based superalloys by electroplating a thin layer of Pt followed by a diffusion treatment at 1150-1175 °C. The Al content in the resulting γ + γ′ coating was in the range of 16-19 at.% on superalloys with 13-14 at.% Al. After oxidation testing, alumina scale adherence to these γ + γ′ coatings was not as uniform as to the β-(Ni,Pt)Al coatings on the same superalloy substrates. To better understand the effect of Al, Pt and Hf concentrations on coating oxidation resistance, a number of Ni-Pt-Al cast alloys with γ + γ′ or β phase were cyclically oxidized at 1100 °C. The Hf-containing γ + γ′ alloys with 22 at.% Al and 10-30 at.% Pt exhibited similar oxidation resistance to the β alloys with 50 at.% Al. An initial effort was made to increase the Al content in the Pt-enriched γ + γ′ coatings by introducing a short-term aluminizing process via chemical vapor deposition or pack cementation. However, too much Al was deposited, leading to the formation of β or martensitic phase on the coating surface.     

Effects of alloying elements on thermal expansions of γ-Ni and γ′-Ni3Al by first-principles calculations

The effects of alloying elements (Al, Cr, Hf, Pt, Y, and Zr) on the coefficients of thermal expansion (CTE) of face-centered-cubic Ni (γ) and L1₂-Ni₃Al (γ′) phases have been investigated in terms of the first-principles quasi-harmonic approach by considering both the vibrational and thermal electronic contributions. By combining the present CTE data and the compositions and phase fractions of γ and γ′, the CTE for some Ni-Al-base alloys are predicted and compared with available experimental measurements in the literature, showing good agreement. It is observed that the addition of Pt is effective in reducing the CTE of both γ and γ′ phases, resulting in lower expansion mismatch between the bond coat and the thermally grown oxide alumina layer, as shown by the predicted CTE of Ni-22 Al-x Pt (at.%) alloys (x = 5, 10, 15, 20, 25, 30).     

Influence of thermal exposure on the stability of metastable microstructures of sputter deposited nanocrystalline 304 and 310 stainless steel coatings

The effect of thermal exposure on the stability of the microstructures of magnetron sputter deposited 304 and 310 stainless steel (SS) coatings have been investigated. The coated 304SS samples were exposed to thermal cycling between 750 °C and room temperature and aged at 500 °C and 650 °C. X-ray diffraction (XRD) results revealed that the microstructures of the as-deposited 304SS and 310SS coatings consisted of αFe + σ and γFe + αFe, respectively. Thermal exposure at 500 °C and 650 °C resulted in the dissolution of σ and partial transformation of αFe into γFe in the 304SS coating and led to the precipitation of σ phase particles, at the expense of αFe, in the 310SS coating. The amount of σ phase in the 310SS coating increased with exposure time. However, both coatings showed no σ phase after thermal cycling to 750 °C for approximately 500 cycles.     

Microstructural evolution of a Ni-based superalloy (617B) at 700 °C studied by electron microscopy and atom probe tomography

We report on the microstructural evolution of a polycrystalline Ni-based superalloy (Alloy 617B) for power plant applications at a service temperature of 700 °C. The formation of secondary M₂₃C₆-carbides close to grain boundaries (GBs) and around primary Ti(C,N) particles is observed upon annealing at 700 °C, where γ′ is found to nucleate heterogeneously at M₂₃C₆ carbides. Using atom probe tomography, elemental partitioning to the phases and composition profiles across phase and grain boundaries are determined. Enrichments of B at γ/M₂₃C₆ and γ′/M₂₃C₆ interfaces as well as at grain boundaries are detected, while no B enrichment is found at γ/γ′ interfaces. It is suggested that segregation of B in conjunction with γ′ formation stabilizes a network of secondary M₂₃C₆ precipitates near GBs and thus increases the creep rupture life of Alloy 617B. Calculations of the equilibrium phase compositions by Thermo-Calc confirm the chemical compositions measured by atom probe tomography.     

Hot corrosion and oxidation behavior of a novel Pt + Hf-modified γ′-Ni3Al + γ-Ni-based coating

A new type of Pt + Hf-modified γ′-Ni₃Al + γ-Ni-based coating has been developed in which deposition involves Pt electroplating followed by combined aluminizing and hafnizing using a pack cementation process. Cyclic oxidation testing of both Pt + Hf-modified γ′ + γ and Pt-modified β-NiAl coatings at 1150 °C (2102 °F), in air, resulted in the formation of a continuous and adherent α-Al₂O₃ scale; however, the latter developed unwanted surface undulations after thermal cycling. Type I (i.e. 900 °C/1652 °F) and Type II (i.e. 705 °C/1300 °F) hot corrosion behavior of the Pt + Hf-modified γ′ + γ coating were studied and compared to Pt-modified β and γ + β-CoCrAlY coatings. Both types of hot corrosion conditions were simulated by depositing Na₂SO₄ salt on the coated samples and then exposing the samples to a laboratory-based furnace rig. It was found that the Pt + Hf-modified γ′ + γ and Pt-modified β coatings exhibited superior Type II hot corrosion resistance compared to the γ + β-CoCrAlY coating; while the Pt + Hf-modified γ′ + γ and γ + β-CoCrAlY coatings showed improved Type I hot corrosion performance than the Pt-modified β.     

Microstructural observations of as-prepared and thermal cycled NiCoCrAlY bond coats

Microstructures of as-prepared and 1100 °C/100 h isothermally annealed NiCoCrAlY bond coat specimens as well as a bond coat obtained from an end of life turbine blade were characterized with TEM. In all specimens the γ grains were observed to consist of fine γ′ precipitates, which form during cooling and are unstable at the higher operating temperatures. The β grains present in the as-prepared specimens were observed to transform to L1₀ martensite in the 1100 °C/100 h isothermally annealed specimen. As a result of substrate-bond coat interdiffusion the M_s temperature increases during thermal cycling due to an increase in Ni and decrease in the Cr concentrations of the β-phase. The turbine blade bond coat was also found to contain Cr and Co-rich σ-phase precipitates.     

Rapid solidification and phase stability evaluation of Ti-Si-B alloys

Ti-rich Ti-Si-B alloys can be considered for structural applications at high temperatures (max. 700 °C), however, phase equilibria data is reported only for T = 1250 °C. Thus, in this work the phase stability of this system has been evaluated at 700 °C. In order to attain equilibrium conditions in shorter time, rapid solidified samples have been prepared and carefully characterized. The microstructural characterization of the produced materials were based on X-ray diffraction (XRD), scanning electron microscopy (SEM-BSE), high resolution transmission electron microscopy (HRTEM), High Temperature X-ray diffraction with Synchrotron radiation (XRDSR) and Differential Scanning Calorimetry (DSC). Amorphous and amorphous with embedded nanocrystals have been observed after rapid solidification from specific alloy compositions. The values of the crystallization temperature (Tx) of the alloys were in the 509-647 °C temperature range. After Differential Scanning Calorimetry and High Temperature X-ray Diffraction with Synchrotron radiation, the alloys showed crystalline and basically formed by two or three of the following phases: αTi, Ti₆Si₂B; Ti₅Si₃; Ti₃Si and TiB. It has been shown the stability of the Ti₃Si and Ti₆Si₂B phases at 700 °C and the proposition of an isothermal section at this temperature.     

Isothermal oxidation behaviour of Nb-W-Cr Alloys

A study of the effect of Cr content on the microstructure and isothermal oxidation behaviour of four alloys from the Nb-Cr-W system has been performed. Selection of specific alloy compositions has been based on the ternary isothermal sections. Oxidation experiments were conducted in air at 900 and 1300 °C for 24 h under isothermal conditions. Weight gain per unit area as function of the temperature has been used to evaluate the oxidation resistance. The phases present in the alloys and the oxide scales were characterized by XRD, SEM, and EDS. Microstructure consists of Nb solid solution and NbCr₂, Laves phase. The oxidation kinetics follows a parabolic behaviour at 1300 °C; the addition of 30% Cr resulted in the significant reduction of the parabolic oxidation rate. At 900 °C, alloys with higher Cr content exhibit higher oxidation rates in comparison to alloys with lower Cr content. The oxidation products are a mixture of CrNbO₄ and Nb₂O₅ and the amount of each oxide present in the mixture is related to the intermetallic phase content and the oxidation temperature. The characterization results delineate the effect of the Cr content on the oxidation mechanisms of these alloys that represent a promising base for high-temperature alloy development.     

Microstructures and liquidus projection of the ternary Ag-Sb-Te system

Ag-Sb-Te alloys are important for thermoelectric applications. Fifty-one Ag-Sb-Te ternary alloys were prepared, and their primary solidification phases were analyzed. The liquidus troughs of the liquidus projection of the ternary Ag-Sb-Te system are determined based on the experimental results and the phase diagrams of the three binary constituent systems. There are 13 primary solidification phase regions. In addition to the three terminal solid solution phases and nine binary compounds, there is one ternary compound, AgSbTe₂. A unique microstructure with bright spherical phases uniformly dispersed in a matrix caused by a miscibility gap in the liquid phase is found in the γ-Ag₂Te primary solidification phase regime. A very fine microstructure with nanometer size Ag₂Te is also observed, resulting from the class I reaction, liquid = δ + Ag₂Te + AgSbTe₂, at 496.5 °C, and the liquid composition of Ag-40.0 at%Sb-36.0 at%Te.     

The effects of heat treatments on hardness and wear resistance in Ni-W alloy coatings

The relationship of processing parameters, microstructure, and mechanical responses of the electrodeposited nickel-tungsten alloys exposed to elevated temperatures in the range 700-1100 °C are investigated. Reverse pulse electrodeposition technique is employed to control the tungsten content and nanocrystalline grain size of the deposits. The application of heat treatment at 700 °C on the alloy with high tungsten content (22 at.%) and small grain size (3 nm) gives hardness enhancement and a small decrease in wear resistance. Prolonging annealing duration and increasing annealing temperature promote more grain growth and reductions of both hardness and wear resistance, despite the formations of secondary phases. For alloys with lower tungsten contents (6% and 13%) and larger grain sizes (13 and 56 nm), higher degrees of grain growth coupled with monotonic decline of hardness are observed. The study indicates that the electrodeposited nickel-tungsten alloys with a high tungsten content potentially serve as strong candidates for high temperature applications.     

Effect of heat treatment on the structure and hardness of high-entropy alloys CoCrFeNiMnV<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> (<Emphasis Type="Italic">x</Emphasis> = 0.25, 0.5, 0.75, 1)

High-entropy alloys CoCrFeNiMnV_{Kharkov Institute of Physics and Technology, ul. Akademicheskaya 1, Kharkov 61108} (Kharkov Institute of Physics and Technology, ul. Akademicheskaya 1, Kharkov 61108 = 0.25, 0.5, 0.75, 1) were prepared by vacuum arc melting. The structure and microhardness of the alloys have been studied in the cast state and after annealing at temperatures of 700–1100°C. It has been found that the alloys consist of the fcc (γ) solid solution and intermetallic sigma (σ) phase. The volume fraction of the σ phase increases with increasing vanadium content. As a result of annealing, phase transformations occur, including the precipitation of σ particles from the γ phase and, vice versa, the precipitation of γ particles from the σ phase. It has been shown that the change in the volume fraction of the σ phase upon annealing occurs due to the changes in the total content of σ-forming elements, chromium and vanadium, in accordance with the lever rule. With increasing temperature, the volume fraction of the σ phase varies nonmonotonically; first, it increases, then it decreases. The microhardness of the alloys correlates well with the change in the volume fraction of the σ phase. The mechanisms of the phase transformations and quantitative relationships between chemical and phase compositions of the alloys and their hardness are discussed.     

High-temperature oxidation behavior of Nb-Si-Cr alloys with Hf additions

The oxidation behavior of two alloys from the Nb-Si-Cr system containing hafnium has been investigated under isothermal and cyclic conditions. Nb-20Si-20Cr-(5,10)Hf alloys (composition in atomic percent) were exposed to air for 24 and 168 h over a range of temperatures from 700 °C to 1400 °C. A gravimetric method was used to determine the oxidation kinetics; weight gain per unit area as a function of temperature or time. Computed isothermal sections of the quaternary Nb-Si-Cr-Hf phase diagrams were used for alloy selection. XRD, SEM and EDS were used to characterize the phases present in the oxidation products and the alloys. Oxidation experiments revealed extremely good oxidation resistance at 700 °C and 800 °C and above 1200 °C under isothermal conditions for both alloys. Partial pesting was observed when the samples were exposed to 800 °C. Complete oxide formation was observed above 1000 °C for 5Hf and above 900 °C for 10Hf up to 1200 °C. Beneficial effects have been observed with the addition of 10Hf to the alloy compared to 5Hf at 700 °C, 1200 °C and 1300 °C resulting in a reduction of weight gain per unit area.     

Experimental determination of the phase equilibria in the Co-Fe-Zr ternary system

The phase equilibria in the Co-Fe-Zr ternary system were investigated by means of optical microscopy (OM), electron probe microanalysis (EPMA), X-ray diffraction (XRD), and differential scanning calorimetry (DSC) on equilibrated ternary alloys. Four isothermal sections of the Co-Fe-Zr ternary system at 1300 °C, 1200 °C, 1100 °C and 1000 °C were experimentally established. The experimental results indicate that (1) no ternary compound was found in this system; (2) the solubility of Fe in the liquid phase of the Co-rich corner at 1300 °C is extremely large; (3) the liquid phase in the Zr-rich corner and the (Co,Fe)₂Zr phase form the continuous solid solutions from the Co-Zr side to the Fe-Zr side; (4) the solubility of Zr in the fcc (Co, Fe) phase is extremely small.     

Phase formation in a Ni-50Cr HVOF coating

A complex, fine scale microstructure of non-equilibrium phases is obtained by HVOF deposition of Ni-50Cr alloy due to the rapid cooling experienced by the splats which make up the as-deposited coatings. XRD analyses indicated that the as-deposited coatings consisted predominantly of a single fcc γ-Ni phase. Two small peaks suggested the presence of NiO and/or NiCr₂O₄ at the limit of detection (∼ 5%). Shoulders on the main γ-Ni peaks were interpreted as evidence of a second, lower Cr content γ-Ni phase. Characterization of the oxide content of the as-deposited coatings by X-ray diffraction, image analysis of backscattered electron images, and electron probe microanalysis yielded conflicting results due to the size of the microstructural features present relative to the spatial resolution of these techniques. Due to the nature and feature size of the non-equilibrium oxide phase(s), direct measurement of the oxygen content by EPMA was found to be the most accurate technique. Heat treatment of an as-deposited coating at 650 °C in vacuum resulted in coarsening of the microstructural features, and an approach towards a mixture of equilibrium phases consisting of γ-Ni, α-Cr, and Cr₂O₃. Evidence was also seen in the XRD pattern of an intermetallic σ phase that has previously only been reported in thin films of Ni-Cr alloys.     

Discontinuous Precipitation of γ′ Phase in Ni-Co-Al Alloys

Decomposition of nickel-base alloys by precipitation of the γ′ phase occurs either continuously (homogeneously) or discontinuously. Under certain conditions of solute content and temperature, discontinuous precipitation is observed. Ni-Al-Co alloys have been characterized by coupling atom probe tomography with transmission electron microscopy studies. The primary focus was to investigate the discontinuous precipitation of γ and γ′ phases. When subjected to fast quenching after solution treatment, the γ′ precipitates exhibit a near-spherical shape and monomodal size distribution with an average size of less than 5 nm. After early stage annealing at 600°C for 10 min, discontinuous precipitation nucleated near the grain boundaries while some regions of homogeneous γ′ precipitates were observed. Discontinuous γ + γ′ product was completely transformed throughout the grain after 600°C/1 h. On long-term annealing (600°C/256 h), coarser γ + γ′ lamellae products replaced the fine discontinuous products that exhibited after 1 h annealing at 600°C. Equilibrium compositions of the γ and γ′ phases were achieved in this coarsening stage. The γ′ phase has an Al content of 25 at.%, which is consistent with the as-quenched condition where the (Ni + Co)₃Al stoichiometry is maintained after 600°C/256 h annealing.     

High temperature oxidation of γ/γ′-strengthened Co-base superalloys

Isothermal oxidation was carried out on new γ/γ′ Co-base superalloys of the system Co–Al–W–B. Appropriate B-contents lead to improved oxidation resistance and oxide layer adhesion. Oxidation at 800 and 900 °C results in formation of Co₃O₄, CoO, and complex oxides (containing Co, Al, and W). A continuous and protective inner alumina layer forms only at 800 °C. Furthermore, oxidation leads to phase transformation (γ/γ′ to γ/Co₃W microstructure) at the matrix/oxide layer interface due to Al-depletion. The effect of additional alloying elements such as Ta, Cr, Nb, Si, V, Mo, and Ir on the oxidation behaviour was also investigated.     

Influence of titanium addition on the microstructure of the novel ferrous-based stainless steel

The microstructural characteristics of the Fe-9Al-30Mn-1C-5Ti (wt.%) alloy were determined by scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectrometry. The microstructure of the alloy was essentially a mixture of (γ + TiC_x + (α + B2 + DO₃)) phases during solution treatment between 950 °C and 1150 °C. The TiC_x carbide had a face-center-cubic structure with a lattice parameter a of 0.432 nm. When the as-quenched alloy was subjected to aging treatment at temperatures of 450-850 °C, the following microstructural transformation occurred: (γ + TiC_x + κ + (α + DO₃)) → (γ + TiC_x + κ + (α + B2 + DO₃ + TiC_x)) → (γ + TiC_x + κ + κ′ + (α + B2 + DO₃)) → (γ + TiC_x + (α + B2 + DO₃)). Addition of Ti promotes the formation of the α phase at high temperatures.     

An in-situ study of plasma nitriding

Direct in-situ observation of phase generation and growth during heat treatment cycles gives information independent e.g. of effects resulting from cooling and atmospheric changes of properties. In this investigation time resolved in-situ X-ray diffraction (XRD) analysis of growing nitride layers during plasma nitriding was conducted to gain experimental data of growing compound layers for different plasma nitriding parameters. With two gas mixtures of 5% N₂-95% H₂ and 25% N₂-75% H₂. plasma nitriding of an AISI 1045 steel was performed in the temperature range of 450 °C < T < 560 °C. The in-situ XRD-observation consisted of series of 50 to 60 single runs of phase analysis during a 3-h plasma nitriding treatment. Nitriding with the formation of nitride phases starts at different times, depending on the nitriding temperature and the gas composition in the plasma for the given plasma parameters pressure, voltage and current density. The higher the nitriding temperature and the higher the nitrogen content in the process gas the shorter is the time for the first detection of the γ′-Fe₄N-phase. Single phase γ′nitride layers were detected for the 5% N₂-95% H₂ gas mixture in a temperature range 450 °C < T < 560 °C. For the highest temperatures 540 °C and 560 °C and the gas mixture 25% N₂-75% H₂ the ε-Fe_2-3N phase occurred later in the plasma nitriding process. Assuming that nitride layers in plasma nitriding also grow by nucleation of small γ′ particles up to a complete layer, the experimental data fitted in a reasonable way in plots calculated for the incubation time of the γ′-phase during gas nitriding.     

Selective dissolution of the γ phase in a binary Ni(γ)/Ni3Al(γ′) two-phase alloy

Selective dissolution of Ni(γ) in a binary Ni(γ)/Ni₃Al(γ′) two-phase alloy was performed in an aqueous electrolyte including 1 wt.% (NH₄)₂SO₄ and 1 wt.% citric acid to obtain a rough, γ′-terminated surface. The electrochemical potential for the selective dissolution was determined from the polarization curves of the γ and γ′ single-phase alloys. The selective dissolution tests proved that γ was precisely removed above 1.7 V_SCE, resulting in the formation of a rough, γ′-terminated surface. Surface analyses revealed that a passive AlO_x, which retarded the dissolution, was preferentially formed on γ′, resulting in a successful selective dissolution.