Degradation behaviour of sputtered Co–Al coatings on superalloy

Degradation behaviour of sputtered Co–Al coatings on Superni-718 substrate has been investigated. Cyclic high temperature oxidation tests were conducted on uncoated and coated samples at peak temperatures of 900 °C for up to 100 thermal cycles between the peak and room temperatures. The results showed that a dense scale formed on the coated samples during thermal cycling at the peak temperature of 900 °C. The external scale exhibited good spallation resistance during cyclic oxidation testing at both temperatures. The improvement in oxide scale spallation resistance is believed to be related to the fine-grained structure of the coating. Nanostructured Co–Al coatings on Superni-718 substrate were deposited by DC/RF magnetron sputtering. FE-SEM/EDS, AFM, and XRD were used to characterize the morphology and formation of different phases in the coatings, respectively. The Co–Al coating on superalloy substrate showed better performance of cyclic high temperature oxidation resistance due to its possession of β-CoAl phase as Al reservoir and the formation of Al₂O₃ and spinel phases such as CoCr₂O₄ and CoAl₂O₄ in scale. The oxidation results confirmed an improved oxidation resistance of the Co–Al coating on superalloy as compare to bare substrate in air at 900 °C temperature up to 100 cycles.     

Microstructure evolution in bulk and surface states of chromium rich nickel based cast alloys reinforced by hafnium carbides after exposure to high temperature air

Abstract

Three alloys based on nickel, with a high level of chromium (25 wt-%) and containing varied quantities of carbon, 0·25 and 0·50 wt-%, and hafnium, 3·7 and 5·6 wt-%, fabricated by casting, were subjected to a 46 h long exposure at 1200°C in dry industrial air. The aim of the work was to investigate the thermal stability of their carbide interdendritic network and to discover their general behaviour in high temperature oxidation. The volume fraction of the hafnium carbides decreased slightly during high temperature exposure but their fragmentation was rather limited. In contrast, chromium carbides appeared in the two alloys, which initially contained exclusively HfC, and this may result in a decrease in their high temperature properties. The evolution of the carbides appeared to be responsible for a moderate lowering of room temperature hardness. The behaviour of the three alloys during high temperature oxidation was very good, despite the unusually high content of hafnium. All were chromia-forming, although oxidation of Hf led to HfO₂ islands in the external scale and in the subsurface region. In summary, the behaviour of these three alloys showed that the HfC containing Ni–25Cr family is potentially interesting for applications at very high temperatures.     

Microstructure and oxidation behaviour at 1100°C of HfC containing Cr rich iron based cast alloys

Three alloys containing 0·25–0·50 wt-%C, 26–28 wt-%Cr and 4–6 wt-%Hf were elaborated by foundry. They contained a dendritic matrix and HfC carbides, which are expected to strengthen the alloy at high temperatures. They were exposed in air at 1100°C during 46 h. The aged microstructures displayed coarsened chromium carbides but no significant changes to the fraction or morphology of the HfC carbides. The surface characterisation of the oxidised samples showed that the alloys behaved well despite some localised instances of fast oxidation. The hardness was modified by the microstructure stabilisation achieved during the high temperature exposure. A preliminary test showed that the reinforcement by HfC may indeed lead to interesting creep resistance at 1100°C as had been hoped.     

Effects of short- and long-term thermal exposures on the stability of a Ni–Co–Cr–Si alloy

Long-term thermal stability is often needed for high temperature alloys used in a variety of industrial applications for extended operating lifetimes. In this paper, the effects of thermal exposures or aging on the mechanical properties and microstructure of a Ni–Co–Cr–Si alloy (HAYNES® HR-160® alloy) were studied. It includes both short- and long-term elevated temperature exposures ranging from 649 °C to 1093 °C (1200–2000 F) for duration of 6 min (0.1 h) to 6 years (50,000 h). The residual room temperature (RT) tensile and Charpy-V impact toughness properties were evaluated and correlated to microstructural changes as well as to fracture surfaces of the tensile tested samples. It was found that the RT ductility and impact toughness of the HR-160 alloy decreased continuously with time. A significant percentage of reduction in the ductility occurred in the initial 1000 h of exposure and the subsequent exposure led only to a minimal loss of ductility and impact toughness values. The concomitant microstructural changes were studied using optical metallography, SEM/EDS and X-ray diffraction of extracted residues. The results presented in this paper demonstrated that the HR-160 alloy exhibits good thermal stability characterized by >16% RT elongation after 50,000 h exposures at 649 °C, 760 °C, and 871 °C.     

Investigation of solidification behavior and associate microstructures of Co–Cr–W and Co–Cr–Mo alloy systems using DSC technique

This article presents a study of solidification behavior and the corresponding microstructure of Co–Cr–W and Co–Cr–Mo alloy systems using the differential scanning calorimetry technique. The influence of main constituents on the solidification behavior and associate microstructures of these alloys are investigated. It is found that chemical composition influences significantly the solidification behavior of cobalt-based alloys. Solution-strengthened alloy has the highest solidification temperature and narrowest solidification range. Presence of carbon decreases the solidification temperature and increases the solidification range. Addition of boron greatly decreases the solidification temperature. Carbon content dominates the solidification behavior of cobalt-based alloys when the contents of the solution-strengthening elements Mo and Ni are within their saturation in the solution matrix. However, as these contents reach a certain level, formation of intermetallic compounds changes the solidification behavior of these alloys remarkably. Increase in the contents of solution-strengthening elements reduces the solid solution transformation temperature and the eutectic temperature when carbon content is constant.     

Electrochemical characterization of oxide formed on chromium containing mild steel alloys in LiOH medium

Flow accelerated corrosion leads to wall thinning of outlet-feeder pipes in the primary heat transport system of pressurized heavy water reactors and can even necessitate enmasse feeder replacement. Replacement of carbon steel 106-grade-B (CS) with chromium containing carbon steel reduces the risk of this failure. This paper discusses the role of small additions of chromium in modifying the properties of the oxide film. CS and chromium containing mild steels viz., A333, 2.25Cr–1Mo and modified 9Cr–1Mo alloy were exposed to primary heat transport (PHT) system chemistry conditions. The oxide films formed were characterized by electrochemical and surface characterization techniques. Mott–Schottky analysis showed donor type of defects. The densities of defects in the oxides of chromium containing alloys were 3–15 times less than that in CS. In presence of ∼200 ppb of dissolved oxygen, the oxides formed were hematite with two orders of magnitude smaller concentration of defects as compared to that formed under reducing conditions. These results suggest that the presence of chromium lowers the defect density of the oxide film and thus ensures a reduced corrosion rate.     

The study of metal ion release and cytotoxicity in Co–Cr–Mo and Ti–Al–V alloy in total knee prosthesis – scanning electron microscopic observation

We surgically retrieved two cobalt(Co)–chromium(Cr)–molybdenum(Mo) and five titanium(Ti)–aluminum(Al)–vanadium(V) alloy knee prostheses from patients because of mechanical failure and pain. We examined the distribution of the small particles which were released from the Co–Cr–Mo and Ti–Al–V alloys using a backscattered scanning electron microscopy (SEM). In addition we analyzed the metals in the artificial knee joints and the tissues adjacent to them using energy dispersive X-ray spectroscopy (EDS). We demonstrated that a myriad of fine particles, produced by the abrasion of both Co–Cr–Mo and Ti–Al–V alloys, accumulated in the synovial cells. As Co–Cr–Mo alloys disintegrate easily in the cells, Co dissolves from the peripheral areas of them, although Cr remains within the cells. In contrast Ti–Al–V alloys are very stable in the synovial cells. From these findings we conclude that the Co–Cr–Mo alloys are hazardous to the body as the alloys release Co which enters the body. In contrast the Ti–Al–V alloys are very stable and are patently safer. Artificial joints, however, are still in considerable need of improvement.     

Effect of silicon content in steel and oxidation temperature on scale growth and morphology

The effect of high silicon content in steel, 1.6 wt.%Si and 3.2 wt.%Si, and high oxidation temperatures (850–1200 °C) on scale growth rate and morphology were investigated. The steels were oxidized in a 15% humid air with short isothermal oxidation times (15 min). The scale growth rate of the non-alloyed steel follows a parabolic law with time; it is an iron diffusion controlled oxidation. The presence of silicon delays scale growth by forming a silica SiO₂ barrier layer at the scale/metal interface, this effect is more important for the steel containing 3.2 wt.%Si and induces a discontinuous scale. Silicon oxides are concentrated at the scale/metal interface; their morphology depends on the oxidation temperature. For temperatures lower than 950 °C, silica is formed. Between 950 °C and 1150 °C, fayalite (Fe₂SiO₄) grains appear in the wüstite matrix close to the scale/metal interface. For temperatures higher than 1177 °C, a fayalite–wüstite eutectic is formed; this molten phase favours iron diffusion leading to high scale growth. After cooling, a continuous fayalite layer with small wüstite grains is obtained at the scale/steel interface.     

Effect of nanocarbides and interphase hardness deviation on stretch-flangeability in 998 MPa hot-rolled steels

By performing various laboratory hot-rolling simulation tests, effective rolling conditions for steel with a composition (mass %) of 0.06C–2.0Mn–0.5Si–0.5Cr–0.2(Ti + Nb + V) was studied. Very remarkable mechanical properties were obtained when the coiling simulation temperature was 650 °C: a hole-expanding ratio of 65%, total elongation of 19%, and ultimate tensile strength of 998 MPa were achieved in the hot-rolled state. These results were associated with the Ti–Nb–V multi-microalloyed carbides (10–50 nm in size) precipitated in the ferrite matrix, and with the minimized deviation in interphase hardness.     

Role of nitrogen addition in stabilizing the γ phase of Biomedical Co–29Cr–6Mo alloy

Three-dimensional atom probe observations and thermodynamic calculations revealed that the mechanism of γ-phase stabilization by N addition in the Co–29Cr–6Mo alloy is different from that in stainless steel: N addition does not lower the free energy of the γ phase in Co–29Cr–6Mo but increases the energy barrier and thus lowers the kinetic rate of the γ → ? transition through the formation of Cr–N short range order.     

Microstructure and tensile properties of metal injection molding Co–29Cr–6Mo–0.23C alloy

The microstructure and tensile properties of a metal injection molding 0.23%C Co–Cr–Mo alloy (F75 alloy) were investigated. The as-sintered microstructure contains a significant amount of carbides, and is modified by solution annealing, the main effect being to reduce the amount of carbides. Ductility and ultimate tensile strength increase significantly, but yield strength decreases with solution annealing. Aging causes both intragranular and intergranular precipitation, which increases hardness and yield strength but decreases ductility excessively. In both as-sintered and solution-annealed conditions, the material displays noticeable work hardenability. By sintering at 1300 °C and solution annealing at 1220 °C, 440 MPa yield strength and 25% elongation at fracture are obtained.     

Nitriding of Co–Cr–Mo alloy in nitrogen

Using the results of a thermodynamic analysis, a Co–Cr–Mo alloy was successfully nitrided in nitrogen at temperatures of 1073–1473 K. The near-surface microstructure of the treated Co–Cr–Mo alloy was characterized using X-ray diffraction, field-emission scanning electron microscopy, electron probe micro-analyzer, and transmission electron microscopy equipped with energy-dispersive X-ray spectroscopy. The results indicated that the highest nitriding efficiency was achieved at the treatment temperature of 1273 K, with the size and coverage of the nitride particles on sample's surface increasing with an increase in the treatment duration. After nitriding at 1273 K for 2 h, numerous nitride particles, consisting of an outer Cr₂N layer and an inner π phase layer, were formed on top of the nitrogen-containing γ phase, and some π phase also precipitated in the alloy matrix at the sub-surface level.     

Bimodal grain size distribution: an effective approach for improving the mechanical and corrosion properties of Fe–Cr–Ni alloys

The effect of nanocrystalline grain size and bimodal distribution of nano- and microcrystalline grain sizes on the oxidation resistance and mechanical properties of Fe-based alloys has been investigated. Nanocrystalline and bimodal Fe–10Cr–5Ni–2Zr alloy pellets, prepared by mechanical alloying route, have been compared with conventional microcrystalline stainless steel alloys having 10 and 20 wt% Cr. Zr addition has been shown to improve the grain size stability at high temperatures. A significant improvement in the ductility of bimodal alloys with respect to nanocrystalline alloys was seen presumably due to the presence of the microcrystalline grains in the matrix. The high temperature oxidation of nanocrystalline and bimodal alloys at 550 °C shows superior oxidation resistance over microcrystalline alloy of similar composition (Fe–10Cr–5Ni) and comparable to that of microcrystalline alloy having twice as much Cr (Fe–20Cr–5Ni). Secondary Ion Mass Spectroscopy depth profiling confirms the hypothesis that nanostructure facilitates the enrichment of Cr at the oxide metal interface resulting in the formation of a passive oxide layer.     

Influence of ageing on wear resistance of an Fe–Mn–Si–Cr–Ni–Ti–C shape memory alloy

To further improve the wear resistance of Fe–Mn–Si–Cr–Ni based shape memory alloys, the effects of ageing at 1123 K with and without pre-deformation at room temperature on the precipitation of second-phase particles and their effects on wear resistance were investigated in an Fe–Mn–Si–Cr–Ni–Ti–C alloy. Results showed that the solution treated Fe–Mn–Si–Cr–Ni–Ti–C alloy exhibited much better wear resistance than the solution treated AISI 321 stainless steel; ageing with pre-deformation improved the wear resistance of Fe–Mn–Si–Cr–Ni–Ti–C alloy more effectively than ageing without pre-deformation, especially under the heavy load condition.     

Chromium carbide laser-beam surface-alloying treatment on stainless steel

In order to improve the resistance to wear, oxidation and corrosion of a stainless steel die, chromium carbide surface-alloying treatment was carried out on a 12 % Cr stainless steel using a CO₂ laser. Cr₃C₂ powder slurry was coated on the stainless steel and then a 3 kW CO₂ laser beam was used to irradiate the specimen. The thickness of surface-alloyed layer was about 0.3 mm and the chromium concentration was about 40 % throughout the alloyed-region. Large amounts of Cr₃C₂ and Cr₇C₃ were also distributed in this alloyed layer. From the results of the isothermal oxidation test at 960 °C for 100 h, it was found that the surface-alloying treatment improved the oxidation resistance by about 100 times due to the distribution of chromium carbides and the increase in the chromium concentration. The results of the cyclic oxidation test revealed that the oxidation layer was very stable on the chromium carbide surface-alloyed region, while it scaled off very easily from the substrate region due to porous oxidation products. The microhardness was about 1100 H_v due to the dispersion and precipitation of chromium carbides in addition to the martensitic structure in the surface-alloyed region. The microhardness did not decrease much, despite heating at 960 °C for 100 h. The chromium carbide surface-alloying treatment improved the wear-resistance greatly, and the results of the wear-resistance test were very consistent with those of the microhardness test.     

A study on the oxidation behavior of HVOF sprayed NiCrAlY–0.4 wt.% CeO2 coatings on superalloys at elevated temperature

The high temperature oxidation behavior of HVOF sprayed ceria added NiCrAlY coatings on superalloys has been studied. Oxidation kinetics of the bare and coated superalloys in air at 900 °C under cyclic conditions was investigated. X-ray diffraction, field emission scanning electron microscope with energy dispersive spectroscopy and X-ray mapping were used to analyse the scales formed on the surface of the oxidised samples. The NiCrAlY–0.4 wt.% CeO₂ coated specimen showed negligible microspalling of the scales. The incorporation of ceria in NiCrAlY powder has contributed to the development of adherent oxide scale, in the coating, at elevated temperature and provided the better oxidation resistance.     

The oxidation of binary alloys of chromium with metals of the first long period

Binary alloys of chromium with titanium, vanadium, manganese, iron, cobalt and nickel respectively have been oxidation-tested in air up to 1100° C. From the results the temperature corresponding to a weight change of 1 mg cm^–2 over 4 h was determined by interpolation, and this temperature has been plotted against composition.With the exception of a 50% cobalt alloy, alloys of chromium with either iron, cobalt or nickel withstand air oxidation at much higher temperatures than the constituent metals. Oxidation resistance in the other systems is generally lower.An additional note describes the determination, during oxidation, of comparative electrical resistance of scales on iron, chromium, and an iron-20% chromium alloy.     

Influence of the phase compositions on the transient-stage high-temperature oxidation behaviour of an NiCoCrAlY coating material

The oxidation behaviour of a commercial NiCoCrAlY coating material (H. C. Starck Inc.; Amperit 410) was investigated in the temperature range 850–1200°C. The measurements were made in air under isothermal and cyclic conditions. The oxidation process was quantified by thermogravimetry. The oxide compositions were characterized by energy-dispersive X-ray analysis (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and secondary-ion mass spectroscopy (SIMS). The corresponding oxide morphologies were studied by scanning electron microscopy (SEM). This study was focused on the oxide growth of a NiCoCrAlY alloy at temperatures between 850 and 1200°C up to oxidation periods of 25 h. Complementary information obtained from various surface-sensitive techniques are summarized in a simplified scheme of the oxide growth. The oxidation behaviour in the stated temperature range is explained by the different chromium and aluminium contents of the phases. Yttrium becomes effective at temperatures above 1000°C. The good protective properties of the NiCoCrAlY at temperatures above 1000°C and the fairly poor protection below 950°C are interpreted in terms of alumina formation and chromia formation as rate-determining factors.     

Proof-testing of hot-pressed silicon nitride

Proof-testing was investigated as a method for insuring the reliability of hot-pressed silicon nitride in high temperature structural applications. The objective of the study was to determine if the strength distribution of a population of test specimens could be truncated by proof-testing. To achieve this objective the strength of silicon nitride was measured at 25° C and 1200° C, both with and without proof-testing. At 25° C, however, the strength distribution was effectively truncated by proof-test ing. At 1200° C, however, the effectiveness of proof-testing as a means of truncating the strength distribution was determined by the resistance of the silicon nitride to oxidation. Although oxidation removes machining flaws that limit the strength of silicon nitride, long-term exposure to high temperature oxidizing conditions resulted in the formation of surface pits that severely degraded the strength. Provided the effects of high temperature exposure are taken into account, proof-testing is shown to be useful for truncating the strength distribution of hot-pressed silicon nitride at elevated temperatures.     

Oxidation behaviour of ledeburitic steels for hot rolls

The oxidation behaviour of two high speed steels (HSS) employed for the production of hot rolls was studied. The steels have slightly different chromium contents and volume fractions of primary carbides. Because oxidation nucleates at the matrix–carbide interfaces and propagates in the matrix without involving the carbides, the oxide scale grows less uniform. All the primary carbides have a higher Cr content than the matrix; therefore they tend to reduce the oxidation resistance. The slight differences in chromium content and in carbide volume fraction are responsible for the different oxidation resistance at 600 and 700°C, whilst at 500°C the two steels have almost the same resistance.