Experimental study and thermodynamic modeling of the Al–Co–Cr–Ni system

A thermodynamic database for the Al–Co–Cr–Ni system is built via the Calphad method by extrapolating re-assessed ternary subsystems. A minimum number of quaternary parameters are included, which are optimized using experimental phase equilibrium data obtained by electron probe micro-analysis and x-ray diffraction analysis of NiCoCrAlY alloys spanning a wide compositional range, after annealing at 900 °C, 1100 °C and 1200 °C, and water quenching. These temperatures are relevant to oxidation and corrosion resistant MCrAlY coatings, where M corresponds to some combination of nickel and cobalt. Comparisons of calculated and measured phase compositions show excellent agreement for the β–γ equilibrium, and good agreement for three-phase β–γ–σ and β–γ–α equilibria. An extensive comparison with existing Ni-base databases (TCNI6, TTNI8, NIST) is presented in terms of phase compositions.     

Experimental study and thermodynamic modeling of the Al–Co–Cr–Ni system

Abstract

A thermodynamic database for the Al–Co–Cr–Ni system is built via the Calphad method by extrapolating re-assessed ternary subsystems. A minimum number of quaternary parameters are included, which are optimized using experimental phase equilibrium data obtained by electron probe micro-analysis and x-ray diffraction analysis of NiCoCrAlY alloys spanning a wide compositional range, after annealing at 900 °C, 1100 °C and 1200 °C, and water quenching. These temperatures are relevant to oxidation and corrosion resistant MCrAlY coatings, where M corresponds to some combination of nickel and cobalt. Comparisons of calculated and measured phase compositions show excellent agreement for the β–γ equilibrium, and good agreement for three-phase β–γ–σ and β–γ–α equilibria. An extensive comparison with existing Ni-base databases (TCNI6, TTNI8, NIST) is presented in terms of phase compositions.     

Microstructure and tribological characteristics of aged Co–28Cr–5Mo–0.3C alloy

In this study, an attempt to investigate the role of isothermal aging on the microstructure and tribological characteristics of Co–28Cr–5Mo–0.3C alloy was made. Regarding the results, isothermal aging at 850 °C and 950 °C for at least 16 h contributed to the formation of lamellar-type carbides at the grain boundary regions. Moreover, at higher aging times (over 16 h), the amount of lamellar-type carbides decreased. The wear properties of as-cast and heat treated samples were determined at 0.5 ms⁻¹ speed several under normal applied loads such as 50, 80, and 110 N. At the lowest applied load (50 N), the samples were isothermally aged at 850 °C for 8 and 16 h and also the ones were aged at 950 °C for 16 h had higher wear resistance probably due to more volume fraction of lamellar-type carbides when compared to as-cast and the other aged samples, but, at higher applied loads (80 and 110 N) due to the formation of adhesive oxide layer on the as-cast sample surface, the wear rate of as-cast samples is lower compared with all heat treated ones.     

Preparation and characterization of pyrolytically deposited (Co–V–O and Cr–V–O) thin films

The metal acetylacetonates of vanadium, cobalt and chromium were prepared from commercial reagents. The corresponding metal acetylacetonates were mixed in desired ratio and deposited on soda lime glass substrate by metal organic chemical vapor deposition technique. Mixed oxides thin films with atomic composition Co_0.31V_1.37O₅ and Cr_0.5V₂O₅ were obtained. A combination of Rutherford backscattering spectroscopy and energy-dispersive X-ray fluorescence was used for the transition element identification and atomic compositional study of the thin films. The thickness of the Co–V–O and Cr–V–O thin films was 166 and 127 nm, respectively. The optical spectra of the films were obtained using a Pye Unicam SP8-400 spectrophotometer in the ultraviolet/visible region. The result of the spectral analyses gave the optical bandgap energy of the materials. The temperature dependence of the electrical resistivity measured using the Van der Pauw method indicated that the materials are semiconducting. Their activation energy was obtained from plots of the natural logarithm of conductivity vs. the reciprocal of temperature. The sign of the thermopower shows that both materials are p-type semiconductors.     

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.     

Mechanical alloying of biocompatible Co–28Cr–6Mo alloy

We report on an alternative route for the synthesis of crystalline Co–28Cr–6Mo alloy, which could be used for surgical implants. Co, Cr and Mo elemental powders, mixed in an adequate weight relation according to ISO Standard 58342-4 (ISO, 1996), were used for the mechanical alloying (MA) of nano-structured Co-alloy. The process was carried out at room temperature in a shaker mixer mill using hardened steel balls and vials as milling media, with a 1:8 ball:powder weight ratio. Crystalline structure characterization of milled powders was carried out by X-ray diffraction in order to analyze the phase transformations as a function of milling time. The aim of this work was to evaluate the alloying mechanism involved in the mechanical alloying of Co–28Cr–6Mo alloy. The evolution of the phase transformations with milling time is reported for each mixture. Results showed that the resultant alloy is a Co-alpha solid solution, successfully obtained by mechanical alloying after a total of 10 h of milling time: first Cr and Mo are mechanically prealloyed for 7 h, and then Co is mixed in for 3 h. In addition, different methods of premixing were studied. The particle size of the powders is reduced with increasing milling time, reaching about 5 μm at 10 h; a longer time promotes the formation of aggregates. The morphology and crystal structure of milled powders as a function of milling time were analyzed by scanning electron microscopy and XR diffraction.     

Wear behavior of carbide coated Co–Cr–Mo implant alloy

The wear behavior of a new type of metal carbide surface coating on Co–Cr–Mo implant alloy was studied. The coating was created using a microwave plasma-assisted reaction. Codeposition of impurity diamond film, diamond particles, and soot was prevented by controlling process conditions. Wear tests were carried out using a sapphire ball-on-Co–Cr–Mo disc unidirectional sliding configuration with harsh conditions of high contact stress and slow sliding speed in both no-lubrication, and deionized water lubrication environments. In the case of uncoated Co–Cr–Mo discs, the effect of deionized water lubrication was remarkable and reduced the wear factor by one order of magnitude compared to the no-lubrication tests. The wear factor of carbide coated Co–Cr–Mo discs was slightly smaller than that of uncoated Co–Cr–Mo discs with deionized water lubrication (2.7×10^–6 mm³N^–1m^–1 vs. 4.2×10^–6mm³N^–;1m^–1). The addition of deionized water lubrication did not greatly affect the wear factor of carbide coated Co–Cr–Mo discs. The influence of surface geometry resulting from the brain coral-like surface morphology of carbide layers on wear behavior was analyzed considering stress concentrations and effective contact area.     

Effect of ball milling on the physical and mechanical properties of the nanostructured Co–Cr–Mo powders

In the present study, Co-based machining chips (P1) and Co-based atomized alloy (P2) has been processed through planetary ball mill in order to obtain nanostructured materials and also to comprise some their physical and mechanical properties. The processed powders were investigated by X-ray diffraction technique in order to determine several microstructure parameters including phase fractions, the crystallite size and dislocation density. In addition, hardness and morphological changes of the powders were investigated by scanning electron microscopy and microhardness measurements. The results revealed that with increasing milling time, the FCC phase peaks gradually disappeared indicating the FCC to HCP phase transformation. The P1 powder has a lower value of the crystallite size and higher degree of dislocation density and microhardness than that of the P2 powder. The morphological and particle size investigation showed the role of initial HCP phase and chemical composition on the final processed powders. In addition results showed that in the first step of milling the crystallite size for two powders reach to a nanometer size and after 12 h of milling the crystallite size decreases to approximately 27 and 33 nm for P1 and P2 powders, respectively.     

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.     

Bend formability and strength of Cu–Be–Co alloys

The effects of addition of 0.01 and 0.03 wt% Mg on the bend formability and strength of a Cu–1.8 wt% Be–0.21 wt% Co alloy aged at 320 °C for 30 min have been investigated metallographically. The addition of Mg to the Cu–Be–Co alloy enhances the bend formability and strength of the alloy. The enhancement of strength is caused by the increase in volume fraction of g_\textI^￠ \gamma_{\text{I}}^{\prime } precipitates in the Cu matrix. In bending of the alloys with and without 0.01 and 0.03 wt% Mg, a number of micro necks first arise along grain boundaries, and part of them grows, resulting in surface wrinkles, which finally lead to surface cracking. The cracking is initiated from voids formed by destruction of bar-like γ precipitates in discontinuous precipitation (DP) cells and propagates along grain boundaries. The addition of Mg decreases the width of DP cells, resulting in better bend formability. This arises because smaller stress concentration due to less inhomogeneous deformation develops in cells and, as a result, destruction of the γ precipitates in cells occurs less easily as the cell width decreases.     

Effects of thermal treatments on protein adsorption of Co–Cr–Mo ASTM-F75 alloys

Post-manufacturing thermal treatments are commonly employed in the production of hip replacements to reduce shrinkage voids which can occur in cast components. Several studies have investigated the consequences of these treatments upon the alloy microstructure and tribological properties but none have determined if there are any biological ramifications. In this study the adsorption of proteins from foetal bovine serum (FBS) on three Co–Cr–Mo ASTM-F75 alloy samples with different metallurgical histories, has been studied as a function of protein concentration. Adsorption isotherms have been plotted using the surface concentration of nitrogen as a diagnostic of protein uptake as measured by X-ray photoelectron spectroscopy. The data was a good fit to the Langmuir adsorption isotherm up to the concentration at which critical protein saturation occurred. Differences in protein adsorption on each alloy have been observed. This suggests that development of the tissue/implant interface, although similar, may differ between as-cast (AC) and heat treated samples.     

The role of cementite in the metal dusting of Fe–Cr and Fe–Ni–Cr Alloys

Abstract

Model Fe–25 w/o (weight percent) Cr and Fe–25 Cr–Ni alloys containing 2.5, 5, 10 and 25w/o nickel were exposed to a CO–26H₂–6H₂O (vol. pct) mixture at 680°C under thermal cycling conditions. The supersaturated carbon activity was calculated to be 2.9 (referred to graphite) and M₃C was predicted to form on Fe–25Cr and Fe–25 Cr–2.5 Ni, but not on higher nickel content alloys. Metal dusting occurred on all alloys, accompanied by internal carburisation. Transmission electron microscopy of the dusting deposit showed that much of the carbon consisted of hollow graphite nanotubes. Small, metal-rich particles were found at the carbon filament tips. These were identified as single crystal Fe₃C in the case of Fe–25 Cr, and M₃C, containing low levels of nickel, in the case of Fe–25 Cr–2.5 Ni and Fe–25 Cr–5 Ni. In contrast, the particles found at the filament tips on the higher nickel, two phase, alloys were both M₃C and austenitic Fe–Ni. Strong orientation relationships were determined between the graphite and cementite particles, however, no consistent and clear crystallographic relationship was deduced between the graphite and austenite particles. It is concluded that carbon deposition from the gas is catalysed by both Fe₃C and austenite. Subsequent carbon nanotube growth reflects the orientation relationship between Fe₃C and the graphite.     

Preparation and properties of WC–Co textured components

Abstract

WC–Co components having one {0001} textured surface have been produced and tested. The textured surface has beenfound to be harder and more resistant to fracture and abrasive wear than standard surfaces. A method is proposed to produce WC–Co components having a bulk {0001} texture.

MST/1337     

Properties and microstructure of WC–TiC–Co and WC–TiC–MO2C–Co(Ni) cemented carbides

Abstract

The present study is an attempt to observe the changes in microstructure and properties of modified WC–10Co cemented carbides from the viewpoint of the distinctive role played by modified binder phase. Introduction of TiC into WC–10Co cemented carbide results in microstructural non-uniformity, i.e. a wide range of grain size distribution, which in turn gives rise to a drastic drop in values of transverse rupture strength and toughness. The modification of binder and carbide phases by incorporating, respectively, nickel and M02C improves the microstructural uniformity, which ensures better mechanical properties. The present findings have been interpreted in terms of various quantitative microstructural parameters, with particular attention being given to the wettability factor.

MST/1363     

Magnetic and dielectric properties of Co–Zn ferrite

Nanocrystalline powders of Co substituted Zn ferrite with the chemical formula Co_xZn_1−xFe₂O₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1) were synthesized by sol–gel autocombustion method using tartaric acid as fuel agent. The samples were sintered in static air atmosphere for 7 h at 773 K, 7 h at 973 K and 10 h at 1173 K. The organic phase extinction and the spinel phase formation were monitored by means of Fourier transform infrared spectroscopy. The X-ray diffraction patterns analysis confirmed the spinel single phase accomplishment. Crystallite size, average grains size, lattice parameter and cation distribution were estimated. Magnetic behavior of the as-obtained samples by means of M-H hysteresis measurements was studied at room temperature. Permeability and dielectric permittivity at room temperature versus frequency was the subject of a comparative study for the Co_xZn_1−xFe₂O₄ series. In agreement with the proposed cation distribution the sample with Co_0.8Zn_0.2Fe₂O₄ formula exhibits the optimal magnetic and dielectric properties.     

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.     

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.     

Thermodynamic characterization of Al–Cr,Al–Zr,and Al–Cr–Zr alloy systems

Abstract

The equilibrium phase diagrams of Al–Cr, Al–Zr, and Al–Cr-Zr, with particular reference to aluminium-rich alloys, have been critically reviewed. On the basis of these, and consistent with measured thermodynamic values, the binary systems have been thermodynamically characterized. Using these characterizations, phase equilibria have been extrapolated in the ternary, with the intention of augmenting the sparse experimental information concerning the equilibrium liquidus (0–10 at.%Cr, Zr) and solid solution range of aluminium in Al–Cr–Zr. Using the same parameters that define the equilibrium phase relationships, metastable phase relationships can also be extrapolated into the ternary.

MST/418     

Electrochemical behaviour of Ti–Ni SMA and Co–Cr alloys in dynamic Tyrode’s simulated body fluid

The electrochemical behaviour of Ti–Ni shape memory alloy and Co–Cr alloys were investigated in dynamic Tyrode’s simulated body fluid on a Model CP6 Potentiostat/Galvanostat. The results indicated that, for all alloys, the anodic dissolution and the pitting sensitivity increased with the flow rate of the Tyrode’s solution increasing while the open-circuit potentials and pitting corrosion potentials decreased with the Tyrode’s solution increasing. Pitting corrosion of Ti–Ni alloy was easier than Co–Cr alloys. Since the solution’s flow enhanced oxygen transform and made it easy to reach the surface of electrodes, the plateau of oxygen diffusion control was diminished. All these indicated that the cathodic reduction and the corrosion reaction, which was controlled by the electrochemical mass transport process, were all accelerated in dynamic Tyrode’s simulated body fluid.     

Effects of Cr Content on the Microstructure and Properties of 26Cr–3.5Mo–2Ni and 29Cr–3.5Mo–2Ni Super Ferritic Stainless Steels

By using scanning electron microscopy,energy-dispersive spectrometry,X-ray diffraction,strength and hardness measurements,the microstructure,precipitation,mechanical properties,and corrosion resistance have been investigated for two super ferritic stainless steels,26Cr–3.5Mo–2Ni and 29Cr–3.5Mo–2Ni,with the aim to consider the effect of Cr content.The results showed that with the addition of Cr content,the recrystallization temperature was increased;the precipitation of Laves and Sigma(σ)phases was promoted and the mechanical properties of super ferritic stainless steel were modified.Furthermore,the pitting corrosion resistance and corrosion resistance to H_2SO_4 of the two super ferritic stainless steels were improved.In addition,suitable annealing processing is a key factor to maintain integrated performance by optimizing microstructure and removing detrimental precipitation phases.