The effect of Ni additions on the oxidation behaviour of Co–Re–Cr high-temperature alloys

Abstract

The present study focused on the influence of Ni on the microstructure and oxidation behaviour of Co–Re–Cr-based alloys. Alloys with three different Ni contents were tested in laboratory air at 800–1100 °C. A refinement and a reduction of the σ phase volume fraction as well as a change in the matrix microstructure were observed. Thermogravimetric measurements showed that the alloys with higher Ni contents possess a better oxidation resistance when exposed to higher temperatures. All alloys suffered from continuous mass loss during oxidation at 800 °C due to the formation of porous oxides scales, consisting of Co₃O₄, Co(Ni)O and Ni-doped CoCr₂O₄, which allow the evaporation of Re-oxides. At 900–1100 °C, only the alloy with 25 at. % Ni showed parabolic oxidation kinetics after a short period of transient oxidation. This is a result of the fast formation of a protective Cr₂O₃ layer. It was also found that exposure to air at 1000 °C leads to a phase transformation of the bulk material; an oxidation-induced formation of fine hexagonal close-packed (hcp) grains was observed near the oxide scales. It is supposed that the improved oxidation resistance of Ni-containing Co–Re–Cr alloys is a result of enhanced Cr diffusion caused by the Ni addition. The extensive formation of the fcc phase in the alloy matrix had a detrimental effect on the oxidation behaviour of the Ni-containing Co–Re–Cr-based alloys.     

Corrosion behaviour of heat treated boron free and boron containing Ti–13Zr–13Nb (wt%) alloy in simulated body fluid

The corrosion behaviour of heat treated Ti–13Zr–13Nb (TZN) and Ti–13Zr–13Nb–0.5B (TZNB) alloys in Hank’s solution has been investigated. The microstructure of the heat treated TZN alloy consisted of α, β or martensite. Addition of boron to TZN alloy led to the formation of dispersed TiB particles and modification of microstructure. In general, the furnace cooled TZN sample showed lower corrosion potential (E_corr) than the air cooled sample. Aging of water quenched samples decreased the E_corr value. The passive current density of TZN samples varied within a narrow range. Presence of boron in TZN alloy decreased the corrosion potential and substantially increased the passive current density. Results showed that boron deteriorated the corrosion resistance of TZN alloy.     

Electrochemical characteristics of nano and microcrystalline Fe–Cr alloys

The electrochemical behavior of nano and microcrystalline Fe–10Cr and Fe–20Cr alloys was determined using potentiodynamic polarization in 0.5 M H₂SO₄. Disks of the alloys were prepared by high-energy ball milling followed by compaction and sintering. In the current study, nanocrystalline Fe–Cr alloys reveal significantly different electrochemical characteristics, typified by lower anodic current densities and more negative passivation potentials, compared with their microcrystalline counterparts. In addition to the differences in grain boundary density, compositional characterization of corrosion films carried out by X-ray photoelectron spectroscopy indicates a higher Cr content in the film developed upon nanocrystalline Fe–Cr alloys. Mechanisms for observed enhancement in the corrosion performance of the nanocrystalline Fe–Cr alloys are discussed.     

Correlation of microstructure and magnetic properties in Cu–Co–Ni alloys

The present study concerns correlation of microstructure and magnetic properties of nanocrystalline binary 50Cu–50Co and ternary 50Cu–25Co–25Ni (wt%) alloys prepared by ball milling and subsequent isothermal annealing of the ball milled alloys. High resolution transmission electron microscopic (HR-TEM) investigation has shown deformation-induced microstructural features. Field emission scanning electron microscopy (FE-SEM) has revealed a distinct change in morphology of as-milled CuCoNi alloys after annealing. Differential scanning calorimetric (DSC) and X-ray diffraction (XRD) analysis have revealed that annealing of the CuCoNi alloy above 350 °C results into precipitation of nanocrystalline Co (fcc) in the CuNi matrix by spinodal decomposition. It is also demonstrated that isothermal annealing of the ball milled alloys in the temperature range between 350 and 650 °C significantly influence the magnetic properties, e.g. coercivity (H_c), remanence (M_r) and magnetic saturation (M_s) due to annihilation of defects such as stacking and twin fault along with dissolution and/or precipitation of magnetic phases in the Cu-rich matrix.     

Tribological behavior of alumina-added apatite–wollastonite glass–ceramics in simulated body fluid

Tribological properties of an alumina-added apatite–wollastonite glass–ceramic produced by controlled heat treatment of a glass in the system MgO–CaO–SiO₂–P₂O₅–Al₂O₃ have been evaluated and compared with those of selected commercial dental ceramics, Duceragold and IPS Empress. Tribological tests were performed in dry condition and in simulated body fluid (SBF) using a pin-on-disk apparatus. The friction coefficient and specific wear rate of the tested materials were measured in dry and in artificial saliva (simulated body fluid: SBF) in order to elucidate the appropriateness of the alumina-added apatite–wollastonite (A–W) glass–ceramic for dental applications. Wear rate of the materials investigated varied from 0.96 × 10⁻⁴ mm³ N⁻¹ m to 41.37 × 10⁻⁴ mm³ N⁻¹ m depending on the bioenvironmental test conditions. The results of this study revealed that the alumina-added A–W glass–ceramic becomes more wear resistant as sintering temperature is increased and exhibits tribological properties similar to those of the commercial dental materials investigated.     

In vitro corrosion behaviour of Ti–Nb–Sn shape memory alloys in Ringer’s physiological solution

The nearly equiatomic Ni–Ti alloy (Nitinol) has been widely employed in the medical and dental fields owing to its shape memory or superelastic properties. The main concern about the use of this alloy derives form the fact that it contains a large amount of nickel (55% by mass), which is suspected responsible for allergic, toxic and carcinogenic reactions. In this work, the in vitro corrosion behavior of two Ti–Nb–Sn shape memory alloys, Ti–16Nb–5Sn and Ti–18Nb–4Sn (mass%) has been investigated and compared with that of Nitinol. The in vitro corrosion resistance was assessed in naturally aerated Ringer’s physiological solution at 37°C by corrosion potential and electrochemical impedance spectroscopy (EIS) measurements as a function of exposure time, and potentiodynamic polarization curves. Corrosion potential values indicated that both Ni–Ti and Ti–Nb–Sn alloys undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Ti–18Nb–5Sn alloy. Significantly low anodic current density values were obtained from the polarization curves, indicating a typical passive behaviour for all investigated alloys, but Nitinol exhibited breakdown of passivity at potentials above approximately 450 mV(SCE), suggesting lower corrosion protection characteristics of its oxide film compared to the Ti–Nb–Sn alloys. EIS studies showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The obtained EIS spectra were analyzed using an equivalent electrical circuit representing a duplex structure oxide film, composed by an outer and porous layer (low resistance), and an inner barrier layer (high resistance) mainly responsible for the alloys corrosion resistance. The resistance of passive film present on the metals’ surface increases with exposure time displaying the highest values to Ti–18Nb–4Sn alloy. All these electrochemical results suggest that Ti–Nb–Sn alloys are promising materials for biomedical applications.     

Solidification microstructures selection of Fe–Cr–Ni and Fe–Ni alloys

The transition of solidified phases in Fe–Cr–Ni and Fe–Ni alloys was investigated from low to high growth rate ranges using a Bridgman type furnace, laser resolidification and casting into a substrate from superheated or undercooled melt. The ferrite–austenite regular eutectic growth, which is difficult to find in typical production conditions of stainless steels, was confirmed under low growth rate conditions. The transition velocity between eutectic and ferrite cell growth had a good agreement predicted by the phase selection criterion. Which of either ferrite or austenite is easier to form in the high growth range was discussed from the point of nucleation and growth. Metastable austenite formation in stable primary ferrite composition was mainly a result of growth competition between ferrite and austenite. For a binary Fe–Ni system, a planar metastable austenite in the steady state, simultaneous growth such as eutectic and banded growth between ferrite and austenite in an initial transient region are confirmed.     

Microstructure and corrosion properties of as sub-rapid solidification Mg–Zn–Y–Nd alloy in dynamic simulated body fluid for vascular stent application

Magnesium alloy stent has been employed in animal and clinical experiment in recent years. It has been verified to be biocompatible and degradable due to corrosion after being implanted into blood vessel. Mg–Y–Gd–Nd alloy is usually used to construct an absorbable magnesium alloy stent. However, the corrosion resistant of as cast Mg–Y–Gd–Nd alloy is poor relatively and the control of corrosion rate is difficult. Aiming at the requirement of endovascular stent in clinic, a new biomedical Mg–Zn–Y–Nd alloy with low Zn and Y content (Zn/Y atom ratio 6) was designed, which exists quasicrystals to improve its corrosion resistance. Additionally, sub-rapid solidification processing was applied for preparation of corrosion-resisting Mg–Zn–Y–Nd and Mg–Y–Gd–Nd alloys. Compared with the as cast sample, the corrosion behavior of alloys in dynamic simulated body fluid (SBF) (the speed of body fluid: 16 ml/800 ml min⁻¹) was investigated. The results show that as sub-rapid solidification Mg–Zn–Y–Nd alloy has the better corrosion resistance in dynamic SBF due to grain refinement and fine dispersion distribution of the quasicrystals and intermetallic compounds in α-Mg matrix. In the as cast sample, both Mg–Zn–Y–Nd and Mg–Y–Gd–Nd alloys exhibit poor corrosion resistance. Mg–Zn–Y–Nd alloy by sub-rapid solidification processing provides excellent corrosion resistance in dynamic SBF, which open a new window for biomedical materials design, especially for vascular stent application.     

XPS study of the process of apatite formation on bioactive Ti–6Al–4V alloy in simulated body fluid

Bioactive Ti–6Al–4V alloy, which spontaneously forms a bonelike apatite layer on its surface in the body and bonds to living bone through this apatite layer, can be prepared by producing an amorphous sodium titanate on its surface by NaOH and heat treatments. In this study, the process of apatite formation on the bioactive Ti–6Al–4V alloy was investigated in vitro, by analyzing its surface with X-ray photoelectron spectroscopy as a function of soaking time in a simulated body fluid (SBF). Thin-film X-ray diffractometry of the alloy surface and atomic emission spectroscopy of the fluid were also performed complementarily. It was found that immediately after immersion in the SBF, the alloy exchanged Na⁺ ions from the surface sodium titanate with H₃O⁺ ions in the fluid to form Ti-OH groups on its surface. The Ti-OH groups, immediately after their formation, incorporated the calcium ions in the fluid to form calcium titanate. The calcium titanate thereafter incorporated the phosphate ions in the fluid to form an amorphous calcium phosphate, which was later crystallized into bonelike apatite. This process of apatite formation on the alloy was the same as on the pure titanium metal, because the alloy formed the sodium titanate free of Al and V by the NaOH and heat treatments. The initial formation of the calcium titanate is proposed to be a consequence of the electrostatic interaction of negatively charged units of titania dissociated from the Ti-OH groups with the positively charged calcium ions in the fluid. The calcium titanate is postulated to gain a positive charge and interact with the negatively charged phosphate ions in the fluid to form amorphous calcium phosphate, which eventually stabilizes into crystalline apatite.     

Electrochemical behaviour of Ti–25Nb–3Mo–3Zr–2Sn biomedical alloy in different simulated physiological environments

The electrochemical corrosion behaviour of biomedical Ti–25Nb–3Mo–3Zr-2Sn (TLM) alloy was investigated in various simulated body fluids at 37±0·5°C utilising potentiodynamic polarisation and current–time curves. The Ti–6Al–4V (TC4) alloy was also investigated to make a comparison. The different simulated body fluids comprised of 0·9%NaCl saline, Hank’s and Ringer’s solution were employed. The effect of heat treatment on the electrochemical behaviour of the TLM alloy was also considered. It was discovered that all the test specimens were passivated once immersed into the simulated body fluids. It was also found that the TLM alloy has poorer corrosion resistance in Hank’s solution, due to the chemical composition of the Hank’s. After different heat treated, the TLM alloy had different phases and microstructure, and the corrosion behaviour of the TLM alloy was different. In this study, after the heat treatment of 760°C/1 h/AC+550°C/6 h/AC, the TLM alloy had better corrosion resistance. Owing to the corrosion resistance of the TLM alloy was influenced by numerous factors, such as microstructure and the chemical composition of electrolyte, the corrosion behaviour of the TLM alloy is complex. By comparing with the corrosion behaviour of the TC4 alloy, the TLM alloy has poorer corrosion resistant than the TC4 alloy under the same conditions. But the current–time curves of the TLM alloy were more stable than these of the TC4 alloy with further experiments, because of the more passivation film on the surface of the TLM alloy.     

Density and viscosity of ternary Cr–Fe–Ni liquid alloys

The density and viscosity of ternary Cr–Fe–Ni liquid alloys have been investigated over a wide temperature range. The density was measured using electromagnetic levitation as a container-less technique, while viscosity was measured by means of a high-temperature oscillating cup viscometer. Although, the concentration dependence of density shows the influence of the second order (binary) interaction parameter in excess volume, the influence of a third order (ternary) interaction parameter in excess volume can be neglected. The temperature dependences of the viscosities are well described by the Arrhenius law. The viscosity increases monotonically as Fe or Cr concentration increases. For constant temperature, the viscosity as a function of iron molar faction can be described by a thermodynamic model using the enthalpy of mixing as input parameter.     

Density and thermal expansion of Cr–Fe, Fe–Ni, and Cr–Ni binary liquid alloys

Densities and their temperature coefficients of liquid Cr–Fe, Fe–Ni, and Cr–Ni binary alloys have been measured containerless using the technique of electromagnetic levitation. Data have been obtained in a wide temperature range including the supercooled region. The density measurements indicate that these binary systems have a small and positive excess volume, whereas the excess free energies are negative. The temperature coefficients of these alloys can be estimated from those of the pure components. Hence, possible contributions from the temperature dependence of the excess volume can be ignored to calculate the temperature coefficient of density.     

Microstructure and internal friction of Ni–Ti alloys absorbing hydrogen

The microstructure and internal friction of Ni–Ti alloys after hydrogen absorption have been investigated by means of optical microscopy, X-ray diffraction, differential scanning calorimetry and low frequency torsional internal friction apparatus. The results show that, after hydrogen absorption, the grains tend to be elongated, and the nucleation and growth of hydrides are mainly concentrated at the grain boundaries. In addition, a new phase ultimately identified as Ti₂NiH_0·5 phase forms after absorption of hydrogen. The hydrogen induced martensite promotes the emergence of a two-stage transformation. However, the growth of hydrides causes a reduction of the hydrogen induced martensite. The hydrides act as strong pinning points, resulting in a dramatic increase in the internal friction. In addition, the marked change of the internal stress, caused by the microscopic strain and the mismatching of the volumes, also improves the internal friction.     

Effect of equal channel angular extrusion on wear and corrosion behavior of the orthopedic Ti–13Nb–13Zr alloy in simulated body fluid

We report investigations on the texture, corrosion and wear behavior of ultra-fine grained (UFG) Ti–13Nb–Zr alloy, processed by equal channel angular extrusion (ECAE) technique, for biomedical applications. The microstructure obtained was characterized by X-ray line profile analysis, scanning electron microscope (SEM) and electron back scattered diffraction (EBSD). We focus on the corrosion resistance and the fretting behavior, the main considerations for such biomaterials, in simulated body fluid. To this end, potentiodynamic polarization tests were carried out to evaluate the corrosion behavior of the UFG alloy in Hanks solution at 37 °C. The fretting wear behavior was carried out against bearing steel in the same conditions. The roughness of the samples was also measured to examine the effect of topography on the wear behavior of the samples. Our results showed that the ECAE process increases noticeably the performance of the alloy as orthopedic implant. Although no significant difference was observed in the fretting wear behavior, the corrosion resistance of the UFG alloy was found to be higher than the non-treated material.     

Effect of phosphorus segregation and Ni2Cr formation on hydrogen embrittlement in 70Ni–30Cr alloys

Abstract

The effects of aging at 773 K on hydrogen embrittlement in Ni–30Cr (wt-%) alloys having two levels of P have been investigated by considering the grain-boundary segregation of impurity atoms and the Ni₂ Cr ordered-phase formation. Aging at 773K suppressed intergraular fracture and reduced the susceptibility to hydrogen embrittlement in the low-P alloy. Such behaviour can be explained in terms of the grain-boundary strengthening caused by the segregation of C atoms. During aging at 773 K, the Ni₂Cr ordered phase formed and the deformation mode changed from wavy slips to coplanar slip with paired dislocations, and then to coplanar slip with microtwins. In the low-P alloy, this change of deformation mode induced step-like cracks which may have occurred by the separation of either the {111} slip planes or the microtwin interfaces. In the high-P alloy, aging for short times caused C segregation to the grain boundaries which suppressed intergranular fracture. However, aging for longer times induced drastic intergranular hydrogen embrittlement because of the grain-boundary segregation of P atoms, which offset the effect of the boundary strengthening caused by C atoms.

MST/177     

Martensitic transformation kinetics and shape memory effect in Co–Ni alloys

Abstract

The shape memory effect (SME) and martensitic transformation kinetics in Co–Ni alloys were studied. The degree of SME decreased with increasing Ni content, and was proportional to the pre-existing ? martensite content, suggesting that the SME in Co–Ni alloys is related to the coalescence of the pre-existing ? plates. Thermal cycling (α ?) increased the ? martensite content, and the SME became greater with an increasing number of thermal cycles. The martensitic transformation kinetics of Co–Ni alloys can be expressed as Y = 1- exp[-0.00526(M _s-25)], where Y is the volume fraction of ? martensite and M _s is the starting temperature of martensitic transformation (°C).     

Microstructural evolution and deformation behaviour of wrought Mg–Al–Zn alloys under dynamic compression

We perform dynamic compression to extruded AZ31 Mg alloys both along and perpendicular to the extrusion direction (ED) at a high strain rate of 1400?s^?1 using split Hopkison pressure bar, and study the microstructure, texture evolution and mechanical anisotropy. We find that the temperature and loading direction play an important role in affecting microstructure evolution and flow stress. The mechanical anisotropy, yield strength and hardening ability are found to decrease with the rise of temperature. Moreover, the grains are also found to be refined remarkably, and the strong basal texture is weakened substantially owing to the dynamic recrystallisation especially in the case where dynamic compression is carried out perpendicular to the ED at 473?K.     

Morphological changes and hardness evolution in Cu–30Ni–5Cr and Cu–45Ni–15Cr spinodal alloys

Abstract

The development of increased strength in Cu–Ni–Cr alloys, compared with binary Cu–Ni alloys, is dependent upon heat treatment. These alloys have compositions which permit them to be solution treated at elevated temperature and then aged at a lower temperature, in a two phase field, to produce hardening. Decomposition into two phases may occur by nucleation and growth or by a spinodal reaction, depending on alloy composition and heat treatment temperature. As part of a more extensive study of ternary Cu–Ni–Cr alloys, the decomposition of Cu–30Ni–5Cr and Cu–45Ni–15Cr (wt-%) has been studied in the spinodal range. The evolution of microstructure has been determined together with the coarsening kinetics for the modulated spinodal decomposition products. Specimens rapid quenched from 1050°C, were aged in the temperature range 300–800°C. The progress of spinodal decomposition was followed via hardness measurements, X-ray diffraction, and scanning and transmission electron microscopy. Modulation wavelengths were measured from both X-ray diffraction patterns and electron micrographs. It was found that during the early stages of aging the modulation wavelength remained constant while the hardness increased continuously. After a certain period of aging, the hardness remained constant at its peak value, while the modulation wavelength increased continuously. The results are consistent with current theories of spinodal decomposition and hardening.

MST/1733     

Electrochemical and mechanical behavior of laser processed Ti–6Al–4V surface in Ringer’s physiological solution

Laser surface modification of Ti–6Al–4V with an existing calcium phosphate coating has been conducted to enhance the surface properties. The electrochemical and mechanical behaviors of calcium phosphate deposited on a Ti–6Al–4V surface and remelted using a Nd:YAG laser at varying laser power densities (25–50 W/mm²) have been studied and the results are presented. The electrochemical properties of the modified surfaces in Ringer’s physiological solution were evaluated by employing both potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) methods. The potentiodynamic polarizations showed an increase in the passive current density of Ti–6Al–4V after laser modification at power densities up to 35 W/mm², after which it exhibited a decrease. A reduction in the passive current density (by more than an order) was observed with an increase in the laser power density from 25 to 50 W/mm². EIS studies at the open circuit potential (OCP) and in the passive region at 1.19 V showed that the polarization resistance increased from 8.274 × 10³ to 4.38 × 10⁵ Ω cm² with increasing laser power densities. However, the magnitudes remain lower than that of the untreated Ti–6Al–4V at OCP. The average hardness and modulus of the laser treated Ti–6Al–4V, evaluated by the nanoindentation method, were determined to be 5.4–6.5 GPa (with scatter <±0.976 GPa) and 124–155 GPa (with scatter <±13 GPa) respectively. The corresponding hardness and modulus of untreated Ti–6Al–4V were ~4.1 (±0.62) and ~148 (±7) GPa respectively. Laser processing at power densities >35 W/mm² enhanced the surface properties (as passive current density is reduced) so that the materials may be suitable for the biomedical applications.     

Electrochemical behaviour of iron—chrome alloys in relation to pitting corrosion

The polarization behaviour and pitting corrosion of Fe-Cr alloys of 7, 13, 18, 24 wt% Cr were studied. Potentiodynamic and galvanostatic measurements were performed in the absence and presence of Cl^–. As the Cr content increases the active dissolution current densities decrease while the passive range and transpassive current densities increase. Polarization parameters gave for the passive transition of the alloys a Cr concentration of -13%. An increase of Cl^– concentration causes the progressive destruction of passivity. It interfered with O₂ evolution, and then destroyed the transpassive region. Still higher Cl^– concentrations initiated pitting corrosion as shown by the oscillations in potential of the galvanostatic polarization curves supported by visual observation. Results are discussed on the basis of competitive adsorption between the aggressive and inhibitor anions for the active sites on the alloys' surface.