Processing and behavior of nanostructured metallic alloys and composites by cryomilling

Recent interest in nanostructured materials stems, not only from their potential use in a variety of applications, but also from the reported discovery of novel fundamental phenomena. The consolidation of cryomilled powder provides a potential pathway towards large scale manufacturing of nanostructured metallic materials. This approach typically engenders the mechanical attrition of powders in liquid nitrogen, followed by consolidation, using established commercial techniques, such as isostatic pressing and extrusion. In this overview paper, published data are reviewed and discussed with particular emphasis on the following topics: nanostructure evolution mechanisms; primary consolidation and secondary processing methods; thermal stability of cryomilled materials; and mechanical behavior of consolidated materials. Recent mechanical behavior data and the associated mechanisms of cryomilled Al alloys are discussed in an effort to shed light into the fundamental behavior of ultrafine grained and nanostructured materials.     

Comparative study of martensitic transformation behavior of NiAlMn and NiAlMnFe high temperature shape memory alloys

A comparative study of microstructure and martensitic transformation (MT) behavior of Ni₅₉Al₁₁Mn₃₀ and Ni₆₀Al₁₉Mn₁₆Fe₅ high temperature shape memory alloys (SMAs) has been performed by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDXS), optical microscopy, and micro-hardness testing. The MT temperature (MTT) of Ni₅₉Al₁₁Mn₃₀ alloy is higher than that of Ni₆₀Al₁₉Mn₁₆Fe₅ alloy, and both alloys’ MTT increases with increasing annealing temperature. The temperature hysteresis and hardness of Ni₅₉Al₁₁Mn₃₀ alloy are smaller than that of Ni₆₀Al₁₉Mn₁₆Fe₅ alloy. The MT behavior of Ni₆₀Al₁₉Mn₁₆Fe₅ is sensitive to aging temperature and its MTT and hysteresis decrease with increasing aging temperature. However, the MT behavior of Ni₅₉Al₁₁Mn₃₀ alloy is not sensitive to aging temperature. The MT stabilization effects appear in both alloys during thermal cycles. This stabilization effect vanishes from the second thermal cycle. The quenched microstructure of Ni₅₉Al₁₁Mn₃₀ and Ni₆₀Al₁₉Mn₁₆Fe₅ alloys is M plus gamma phase, in which the volume fraction of gamma phase is about 40 and 20%, respectively, and the microhardness of M is higher than that of gamma phase. No aging effects were found in both alloys after aging at 400 °C.     

Hardening behavior of three metallic alloys under combined stresses at elevated temperature

Summary. Initial and subsequent yield loci for type 316 stainless steel, Haynes 188, and Inconel 718 are determined experimentally in the axial-shear stress plane at 650 C. Each of these materials has a face centered cubic (fcc) crystal structure, but entirely different chemical compositions and strengthening mechanisms. Material hardening behavior is described along three cyclic strain paths having a maximum equivalent strain of 0.015 m/m: fully reversed axial (Path I), fully reversed shear (Path II), and a nonproportional hourglass shaped path (Path III). Yielding is defined by a Mises-type equivalent offset strain definition having a target value of 30 m/m. These types of yield surface determination tests are difficult, but fairly common in lower temperature ranges where precision strain gages can be used. Due to the high temperature in this study, axial and shear strains were measured by an extensometer. These results, which describe material hardening by the evolution of size, shape, and position of the current yield surface can be used in support of constitutive models for high temperature metallic materials. Hardening behavior of all three alloys is well described by a mixed hardening rule comprised of isotropic, kinematic, and distortional components. Relative to published work at lower temperatures, the isotropic hardening component is larger and the distortional hardening component is smaller than anticipated.     

Comparative study on the corrosion behavior of Ti-Nb and TMA alloys for dental application in various artificial solutions

The corrosion behavior of Ti-Nb dental alloy in artificial saliva with and without the addition of lactic acid and sodium fluoride was investigated by electrochemical techniques, with the commercial Titanium-molybdenum alloy (TMA) as a comparison. The chemical composition, microstructure and constitutional phase were characterized via energy dispersive spectrometry, optical microscope and X-ray diffraction, meanwhile the open circuit potential, electrochemical impedance spectroscopy and potentiodynamic polarization measurements were carried out to study the corrosion resistance of experimental alloys, with the corroded surface being further characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. It was found that the corrosion behavior of Ti-Nb alloy was similar to those TMA alloy samples in both artificial and acidified saliva solutions, whereas statistical analysis of the electrochemical impedance spectroscopy and polarization parameters showed Ti-Nb alloy exhibited better corrosion resistance in fluoridated saliva and fluoridated acidified saliva. SEM observation indicated that TMA alloy corroded heavily than Ti-Nb alloy in fluoride containing saliva. XPS surface analysis suggested that Nb₂O₅ played an important role in anti-corrosion from the attack of fluoride ion. Based on the above finding, Ti-Nb alloy is believed to be suitable for the usage in certain fluoride treated dental works with excellent corrosion resistance in fluoride-containing oral media.     

Modelling the semisolid processing of metallic alloys

Semisolid processing of metallic alloys and composites utilises the thixotropic behaviour of materials with non-dendritic microstructure in the semisolid state. The family of innovative manufacturing methods based on this behaviour has been developing over the last 20 years or so and originates from scientific work at MIT in the early 1970s. Here, a summary is given of: routes to spheroidal microstructures; types of semisolid processing; and advantages and disadvantages of these routes. Background rheology and mathematical theories of thixotropy are then covered as precursors to the main focus of the review on transient behaviour of semisolid alloy slurries and computational modelling. Computational fluid dynamics (CFD) can be used to predict die filling. However, some of the reported work has been based on rheological data obtained in steady state experiments, where the semisolid material has been maintained at a particular shear rate for some time. In reality, in thixoforming, the slurry undergoes a sudden increase in shear rate from rest to 100 s⁻¹ or more as it enters the die. This change takes place in less than a second. Hence, measuring the transient rheological response under rapid changes in shear rate is critical to the development of modelling of die filling and successful die design for industrial processing.The modelling can be categorised as one-phase or two-phase and as finite difference or finite element. Recent work by Alexandrou and coworkers and, separately Modigell and coworkers, has led to the production of maps which, respectively summarise regions of stable/unstable flow and regions of laminar/transient/turbulent fill. These maps are of great potential use for the prediction of appropriate process parameters and avoidance of defects. A novel approach to modelling by Rouff and coworkers involves micro-modelling of the `active zone' around spheroidal particles. There is little quantitative data on the discrepancies or otherwise between die fill simulations and experimental results (usually obtained through interrupted filling). There are no direct comparisons of the capabilities of various software packages to model the filling of particular geometries accurately. In addition, the modelling depends on rheological data and this is sparse, particularly for the increasingly complex two-phase models. Direct flow visualisation can provide useful insight and avoid the effects of inertia in interrupted filling experiments.     

Comparative study of some metallic biomaterials used as implants

The electrochemical behavior of two Ti alloys (TA and TAV) and two grades of stainless steels (SS₁ and SS₂), commonly used as biomedical implant materials, particularly for orthopedic and osteosynthesis applications, was investigated in Hank's solution at 37 °C and different pH. The aim was to distinguish between the behavior of these materials in artificial physiological solution through analysis of their corrosion potential variation with time and potentiodynamic polarization curves. Characterization of the modified surface layers was made by means of microscopic examinations, hardness measurements and X‐ray diffraction analysis. The results indicated that in neutral Hank's solution (pH = 7.2) SS₂ and SS₁ samples were of higher corrosion resistance than titanium alloys. The behavior was reversed in the acidic media (pH = 5.0 or 3.0), where TA had the least corrosion rate and the corrosion susceptibility increased in the order TA < TAV < SS₁ < SS₂.     

Determination of the thermal conductivity of amorphous metallic alloys

Two techniques are suggested for identifying the temperature dependence of the thermal conductivity of a new class of materials. The results have been obtained for the metallic glass Co₇₇Fe₄Cr₇Si₈B₄.Institute for the Problems of Mechanical Engineering, Kharkov. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 63, No. 3, pp. 314–320, September, 1992.     

Rapid eutectic growth of undercooled metallic alloys

On leave from the Northwestern Polytechnical University, People's Republic of China.     

Comparative study of spinodal decomposition in symmetric and asymmetric Cu-Ni-Cr alloys

Spinodal decomposition in three alloys of nominal compositions 71Cu-27Ni-2Cr, 45Cu-45Ni-10Cr and 33Cu-52Ni-15Cr were studied by X-ray diffraction technique and transmission electron microscopy. It was found that the first and third alloys are asymmetric in nature while the second is symmetric. The symmetric alloy was found to decompose faster than the asymmetric ones. The asymmetry of the side bands was found to be related to the proportion of phases in the alloy. Electron microscopic studies revealed that during coarsening the major phase increases its connectivity by isolating the minor phase.     

Friction and solid-solid adhesion on complex metallic alloys

The discovery in 1987 of stable quasicrystals in the Al–Cu–Fe system was soon exploited to patent specific coatings that showed reduced friction in ambient air against hard antagonists. Henceforth, it was possible to develop a number of applications, potential or commercially exploited to date, that will be alluded to in this topical review. A deeper understanding of the characteristics of complex metallic alloys (CMAs) may explain why material made of metals like Al, Cu and Fe offers reduced friction; low solid–solid adhesion came later. It is linked to the surface energy being significantly lower on those materials, in which translational symmetry has become a weak property, that is determined by the depth of the pseudo-gap at the Fermi energy. As a result, friction is anisotropic in CMAs that builds up according to the translation symmetry along one direction, but is aperiodic along the other two directions. A review is given in this article of the most salient data found along these lines during the past two decades or so.     

Growth and coalescence of penny-shaped voids in metallic alloys

The growth and coalescence of penny-shaped voids resulting from particle fracture is a common damage process for many metallic alloys. A three steps modeling strategy has been followed to investigate this specific failure process. Finite element cell calculations involving very flat voids shielded or not by a particle have been performed in order to enlighten the specific features of a damage mechanism starting with initially flat voids with respect to more rounded voids. An extended Gurson-type constitutive model supplemented by micromechanics-based criteria for both void nucleation and void coalescence is assessed for the limit of very flat voids towards the FE calculations. The constitutive model is then used to generate a parametric study of the effects of the stress state, the microstructure and the mechanical properties on the ductility. Based on these results, a simple closed-form model for the ductility is finally proposed. The main outcomes of this study are that (i) the ductility of metal alloys involving penny-shaped voids is primarily controlled by the relative void spacing; (ii) the definition of an effective porosity in terms of an equivalent population of spherical voids is valid for low particle volume fraction; (iii) the presence of a particle shielding the void does not significantly affect the void growth rates and void aspect evolution; (iv) early fracture by void coalescence can occur under very low stress triaxiality conditions if the particle volume fraction is large enough, explaining that some alloys and composites can fail through a transgranular ductile fracture mode under uniaxial tension condition before the onset of necking; (v) the fracture mechanism moves from void growth controlled to void nucleation controlled when increasing the void nucleation stress, lowering the stress triaxiality, and increasing the initial void aspect ratio.     

脉冲反转技术在金属疲劳损伤非线性超声检测中的应用

材料性能退化总是伴随着某种形式的材料非线性力学行为,从而引起超声波传播的非线性,即高频谐波的产生。研究了利用脉冲反转技术测量金属材料超声学非线性系数的实验方法和信号处理算法,发展了一套可靠的测试实验系统,在相同条件下测量了同一试样在不同输入电压下的二次谐波和基波幅度,二次谐波幅度和基波幅度的平方近似成线性关系,表明实验系统是可靠的。利用该系统进行了一组LY12铝合金疲劳试样非线性超声检测实验。实验结果表明,超声非线性系数可以表征镁合金的疲劳早期退化,脉冲反转技术能够有效提取二次谐波时域信号,增强二次谐波的幅度,抑制主要由实验系统所产生的奇次谐波分量,为材料和结构早期力学性能退化的无损检测和评价提供一种有效的方法。     

Basal-plane stacking-fault energies of Mg alloys: A first-principles study of metallic alloying effects

Generalized stacking-fault energies (GSFEs) of basal-plane stacking faults I₁ and I₂ in Mg alloys have been studied based on first-principles calculations, where 43 alloying elements were considered. It is found that the most contributing features of alloying elements to GSFEs are bulk modulus, equilibrium volume, binding energy, atomic radius and ionization energy. Both bulk modulus and ionization energy exhibit positive relationships with GSFEs, and the others show opposite relationships. Multiple regressions have been performed to offer a quantitative prediction for basal-plane GSFEs in Mg-X systems. GSFEs, alloying effects of elements and the prediction model established within this work may provide guidelines for new Mg alloys design with better ductility.     

Comparative corrosion study of Ag-Pd and Co-Cr alloys used in dental applications

The electrochemical behaviour of two Ag-Pd alloys (Unique White and Paliag) used in dental prosthetics construction for crowns and bridges and one Co-Cr alloy (Vitallium 2000) was studied in artificial saliva using the polarization curves and electrochemical impedance spectroscopy (EIS). The corrosion resistance was evaluated by means of the corrosion currents value and by coulometric analysis. The open circuit potential of Ag-Pd are attributed to dealloying followed by surface enrichment with Ag and the possible formation of an insoluble AgCl surface film on the respective alloy surfaces. Our results have shown that these alloys have a somewhat good corrosion resistance in artificial saliva. The corrosion current densities of Unique White and Vitallium 2000 alloys were very low (∼100 nA/cm²). For Ag-Pd alloys, when increasing the content of Cu, corrosion resistance decreases. The passivation of all samples occurred spontaneously at the open circuit potential. The electrochemical properties of the spontaneously passivated electrodes at the open circuit potential were studied by EIS. The polarization resistance (R _p) and the electrode capacitance (C _dl) were determined. The polarization resistance of all the samples increases with the immersion time. The polarization resistances are largest for Unique White (Ag-Pd) and Vitallium 2000 (Co-Cr) alloys. Because the electrochemical behaviour of the Co-Cr alloy was compared with that of Ag-Pd alloy, this type of alloy may be a suitable alternative for use in the manufacture of fixed dental prostheses. The present study, though limited, has shown that electrochemical characteristics can be used to identify such alloys. Knowledge of the in vitro corrosion behaviour of these alloys may lead to better understanding of any biologically adverse effects in vitro.     

Stress generation during high-temperature oxidation of metallic alloys

During high-temperature oxidation, constraint stresses are generated in the growing oxide in response to a lateral growth strain mechanism. Substantial progress has been made in recent years in clarifying the mechanisms of oxide growth that sets the stage for understanding the origin of the lateral growth strain. Nevertheless, identification of the lateral growth mechanisms remains elusive.     

Equi-axed growth and related segregations in cast metallic alloys

Full-scale trials of DC ingots and laboratory scale directional solidification experiments have been performed to study the effect of grain structure on macro-segregation in industrial cast products. An Al alloy sheet ingot was cast with constant casting conditions (speed, superheat, cooling rate) except for the grain refiner: the first half of the ingot was non-inoculated, while the second half was inoculated. The results indicate that the extent and intensity of the centreline segregation is modified via the grain-refinement treatment: the finer the grains are, the more intense is the macro-segregation.Numerical simulations of directional solidification of binary Al–Cu alloys have been carried out with the help of a 2D finite volume software which takes account of the movement of the liquid with respect to the solid in the mushy zone. It is possible to account for the segregation pattern of the directionally solidified ingots that exhibit columnar or coarse equi-axed grain structures. Contrarily, the intense segregation of the fine-grained ingots is not yet understood.     

Processing of immiscible metallic alloys by rheomixing process

Abstract

Mixing immiscible alloys has been a long standing challenge to both materials scientists and processing engineers. Despite great efforts made worldwide, including extensive space experiments, no casting techniques so far can produce the desirable fine and uniform dispersed microstructure. Based on extensive experience in mixing immiscible organic liquids offered by the polymer processing community, the authors have successfully developed a rheomixing process for mixing immiscible alloys. The rheomixing process utilises first the intensive shear stress-strain field offered by a twin screw extruder to create a fine homogeneous liquid dispersion within the miscibility gap and then the viscous force offered by a semisolid slurry at a temperature below the monotectic temperature is used to counterbalance the gravitational force and the Marangoni effect. A laboratory scale rheomixer has been designed and constructed to realise this two step mixing strategy. The Ga–Pb and Zn–Pb systems were selected to demonstrate the principles of rheomixing. The experimental results showed that the rheomixing process developed is capable of creating a fine and uniform microstructure from immiscible alloys. This paper describes the rheomixing process in detail and the preliminary experimental results on rheomixing in the Ga–Pb and Zn–Pb systems are discussed.     

Fast diffusion and metallic glass formation in zirconium-metal alloys

In this work it was found for a range of zirconium-metal alloys that the differences in atomic size, eIectronegativity and valence of the metals with respect to zirconium, and the extent of the mutual solid solubility act as phenomenological connections between the fast diffusion of the metal in zirconium and the ability of the zirconium-metal alloy to form glasses. It was found that all the alloys of zirconium which exhibit fast diffusion are also able to form glasses. Only metallic glasses obtained by rapid quenching from the melt were considered. The analysis was performed using two criteria to evaluate the glass-forming ability of the alloy, the criteria to ascertain those metals that can behave as fast-diffusing solutes in zirconium and the data for heterodiffusion in zirconium.     

Equi-axed growth and related segregations in cast metallic alloys

Full-scale trials of DC ingots and laboratory scale directional solidification experiments have been performed to study the effect of grain structure on macro-segregation in industrial cast products. An Al alloy sheet ingot was cast with constant casting conditions (speed, superheat, cooling rate) except for the grain refiner: the first half of the ingot was non-inoculated, while the second half was inoculated. The results indicate that the extent and intensity of the centreline segregation is modified via the grain-refinement treatment: the finer the grains are, the more intense is the macro-segregation.

Numerical simulations of directional solidification of binary Al-Cu alloys have been carried out with the help of a 2D finite volume software which takes account of the movement of the liquid with respect to the solid in the mushy zone. It is possible to account for the segregation pattern of the directionally solidified ingots that exhibit columnar or coarse equi-axed grain structures. Contrarily, the intense segregation of the fine-grained ingots is not yet understood.