Age-hardening and the associated phase transformation in an Au-55.2 at% Cu-17.4 at% Ag ternary alloy

To develop a low gold content dental alloy, age-hardening characteristics in an Au-55.2 at% Cu-17.4 at% Ag alloy were studied by means of hardness, electron microscopy and X-ray diffraction examination. Three distinct age-hardening behaviours depending on temperature were found in the alloy, i.e. (i) a dual mechanism of spinodal decomposition and Cu₃Au ordering below 673 K, (ii) a single mechanism of spinodal decomposition at 693 K, and (iii) a single mechanism of nucleation and growth of silver-rich precipitate at 773 K. A marked over-ageing was observed by lengthy ageing over the whole range of temperature. The long-period superstructure of Cu₃Au(II) was found only in the grain boundary product at temperatures between 623 and 633 K.     

Characteristics of the continuous coarsening and discontinuous coarsening of spinodally decomposed Cu-Ni-Fe alloy

The spinodal decomposition and coarsening reaction of a 45Cu-30Ni-25Fe alloy aged with and without prior 75% cold rolling have been studied by Vickers hardness tester, X-ray diffraction, optical microscope, and scanning and transmission electron microscopes. Spinodal decomposition took place in the alloys aged in the temperature range of 600–950°C without prior deformation, and then spinodal structure in these alloys would coarsen only continuously. Spinodal decomposition and continuous coarsening reaction of spinodal structure took place in the alloys aged at lower temperature with prior deformation. This process was corresponding to recovery of spinodal structure in the deformed alloys. Discontinuous coarsening reaction of spinodal structure would also take place in the alloys aged at higher temperature with prior deformation. This process was corresponding to recrystallization of spinodal structure in the deformed alloys.     

Age-hardening behaviour of a spinodally decomposed low-carat gold alloy

The age-hardening behaviour of a spinodally decomposed low-carat gold alloy was investigated by means of hardness test, X-ray diffraction (XRD), field emission scanning electron microscopic (FESEM) observations, and energy dispersive spectrometer (EDS). An apparent hardness increase occurred at the initial stage of the aging process without incubation periods. Then, after a plateau, the hardness increased to the maximum value, and finally, the softening by overaging occurred. The age-hardening of the specimen is characterized by the fast increasing rate in hardness and the apparent delay of softening. By aging the solution-treated specimen, the fcc α₀ phase was transformed into the Ag-rich α₁, Cu-rich α₂, and Zn–Pd-rich β phases through the spinodal decomposition process and the metastable phase formation. The first hardening stage which occurred during the early stage of spinodal decomposition without an apparent structural change was thought to be due to the interaction of dislocation with solute-rich fluctuations. The second hardening stage after the plateau was caused by the formation of the fine block-like structure with high coherency induced by the spinodal decomposition, which corresponded to the phase transformation of the metastable Ag-rich phase into the stable Ag-rich α₁ phase. The remarkably delayed softening was caused by the slow progress of coarsening and resultant chaining of the Ag-rich α₁ precipitates in the Cu-rich α₂ matrix due to the uniform fine scale of the structure.     

Studies on spinodal decomposition in Cu-27Ni-2Cr alloy

Transformation characteristics of a Cu-27Ni-2Cr alloy were studied on ageing in the temperature range of 773 to 1073 K, by means of X-ray diffraction and transmission electron microscopy. It was concluded from morphological features that the alloy undergoes spinodal decomposition and the coherent spinodal was estimated to be 946 K. Yield stress increment on ageing was found to follow monotonically the strain amplitude and to be independent of the wavelength of composition modulation.     

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     

Mössbauer spectrometry study of early stage spinodal decomposition in Fe-Cr-Co alloy under high magnetic field

Local structure in a low-cobalt-type Fe-25Cr-12Co-1Si ferromagnetic alloy spinodal decomposed under an external magnetic field up to 120 kOe was investigated by Mössbauer spectrometry. The high magnetic field was found to significantly affect the local structure in the alloy formed at the early stage of phase decomposition. It was found that high magnetic field favors the acceleration of phase decomposition of ferromagnetic alloy at the early stage, resulting in the enhancement of average hyperfine field. The effect of high magnetic field on spinodal decomposition in ferromagnetic alloy was initially interpreted based on the free energy analyses.     

Age-hardening associated with ordering and spinodal decomposition in a AgCu-40 at % Au pseudobinary alloy

The age-hardening mechanism in an AgCu-40 at% Au alloy was studied by means of electrical resistivity measurement, hardness tests, X-ray diffraction and electron microscopy. Two stages of hardening were found by isothermal ageing below 648 K, which was higher than the critical temperature of ordering, T _c=620 K, in the present alloy. The first stage of hardening took place by formation of a modulated structure resulting from spinodal decomposition. Further hardening was brought about by ordering, yielding metastable AuCu I and/or AuCu II ordered platelets grown from the copper-rich portion of the modulated structure. Transitional ordering which gave rise to a marked hardening of the second stage was found, even though the temperature of below 648 K was higher than the T _c of the present alloy. Drastic softening was also found on disappearance of the transitional ordered phases. Although the modulated structure was observed by ageing at 773 K, there was no age-hardening.     

On the mechanics of large inelastic deformations: kinematics and constitutive modeling

Summary In this paper we examine the complexities associated with the kinematics of finite elastoplastic deformations and other issues related to the development of constitutive equations. The decomposition of the total strain and strain rate tensors into elastic and plastic constituents is investigated by considering both a multiplicative decomposition of the deformation gradient and an additive decomposition of the deformation vector field. Physically based definitions for the elastic and plastic strain rate tensors are given and compared with other values found in the literature. Constitutive equations for the plastic flow are derived by considering both a phenomenological-energy approach and a physically motivatedmesomechanical approach based on the double-slip idealization. It is shown that by resorting to the mechanics of the double slip, specific relations for the plastic stretching and plastic spin can be rigorously derived, taking into account the effect of noncoaxiality and material rotation. Finally, the implication of such effects to large deformations is examined in connection with the localization phenomenon.     

Effects of pressure and vibration on the thermal decomposition of cubic Ti1-x Al x N, Ti1-x Zr x N, and Zr1-x Al x N coatings: a first-principles study

Thermodynamic properties as well as the miscibility gap (binodal) and spinodal decompositions of the cubic Ti_1-x Al _x N, Ti_1-x Zr _x N, and Zr_1-x Al _x N coating alloys have been computed using first-principles calculations. Herein, the cluster expansion method and especially the special quasirandom structure are employed to describe the disordered alloys. The effects of pressure and lattice vibration on the miscibility gaps and spinodal decompositions of the above alloys have been investigated by means of Helmholtz free energy with the vibrational contribution depicted with the Debye-Grüneisen model. It is found that the application of hydrostatic pressure promotes the isostructural decomposition of Ti_1-x Al _x N, Ti_1-x Zr _x N, and Zr_1-x Al _x N alloys, whereas the vibrational contribution decreases the consolute temperature of the phase separation. Our results indicate that the improved age-hardening behavior of cubic Ti_1-x Al _x N coatings with the addition of Zr arises from the enlarged composition range of binodal and spinodal curves at specified temperatures. Our results are in good agreement with the available experimental data and provide a useful insight into the investigation of age-hardening and characterization of Ti–Al–Zr–N-based coatings for high-temperature applications.     

Small-angle scattering from GP zones in Al-Cu alloy

It is well known that Guinier Preston (GP) zones form in Al-Cu alloys upon solutionizing and artificial aging, which are extensively used in commercial practice. It is well established that GP zones are discshaped precipitates, i.e. disks of clusters of copper atoms in the FCC aluminium matrix. These disks have coherency strain fields in aluminium that give the alloy its high yield strength. The formation of GP zones in the supersaturated aluminium matrix is thought to be heterogeneous nucleation and growth. Some authors have believed that the formation of GP zones is by spinodal decomposition of the supersaturated Al-Cu solid solution. The main objective of the present work is to test whether spinodal decomposition is responsible for the formation of GP zones in Al-Cu alloy. The experimental alloy AA2219 was selected for its high copper content (Al-6%Cu-0·2%Zr). After solutionizing and artificial aging, the aging curve was plotted and small-angle scattering experiments were carried on the powdered samples as a function of time during artificial aging. Small-angle scattering data were analysed, and evidence has been obtained for the occurrence of spinodal decomposition as the mechanism responsible in the early stages of formation of GP zones.     

Origin of Ordering Coupled Tweed Microstructures in Alloys with Large Atomic Size Factors

A theoretical study is developed on the evolution and mechanism of an ordering coupled phase separation, and on the origin of a resultant tweed microstructure. It is found that long-range elastic interaction among atoms with different atomic sizes plays a key role in the phase sep aration, and that the evolution of the phase separation is very similar to that Of conventional spinodal decomposition except that the separation is dependent on an elastic interaction order ing (EIO). This "EIO coupled spinodal decomposition" is shown to exhibit a periodical or tweed microstructure being accompanied by an EIO. It is also found that a large atomic size factor yields a large positive contribution of EIO to spinodal decomposition. Generally it is thermodynamically and kinetically favorable for the EIO to precede the onset of spinodal decomposition,though the former is not separable from the latter as a whole. We suggest that an initially disordered solid solution undergoes an EIO first, and then the partially ordered solid solution starts to decompose via a spinodal mechanism. Solute-enriched regions increase their degree of order along with an increase in solute content, and solute-depleted regions decrease their degree of order together with a decrease of solute content. The final microstructure is characterized by a periodical array of highly ordered solute-enriched regions and nearly disordered solute-depleted regions. The notion of EIO coupled spinodal decomposition is in general agreement with the transformation behaviour of a large number of alloy systems.     

Decomposition behaviours of dopant-free and doped solid solutions in the TiO2-SnO2 system

Decomposition behaviours, including phase separation by the spinodal mechanism, were investigated for selected compositions ofx = 0.7, 0.5 and 0.3 in Ti _x Sn_1–x O₂ alloy. Inside the coherent spinodal, an equimolar alloy was found to decompose most rapidly at 1100° C and the decomposition rate decreased as the annealing temperature increased. The difference in the rate of decomposition outside the spinodal betweenx = 0.7 andx = 0.3 alloys suggested that the ionic mobility of diffusing tin was much slower than that of titanium in the alloy system. The effect of some dopants on the decomposition rate was also examined. Doping with tungsten or antimony atoms strongly suppressed the phase separation both inside and outside the spinodal, especially resulting in a prolonged stabilization ofx = 0.7 alloy. The role of the dopants in affecting the decomposition rate is discussed in relation to selective substitution of the doping atoms in the tin or titanium sublattice.     

Theoretical estimation of the effect of interfacial energy on the mechanical strength of spinodally decomposed alloys

New interfaces are produced on the slip plane when a crystal with continuous composition fluctuation arising from spinodal decomposition is deformed by slip. In this work, the energy of such interfaces is evaluated for both modulated and mottled structures, and their effects on slip behaviour are discussed. It is concluded that the contribution of this interfacial energy is large enough to account for the age-hardening concomitant with spinodal decomposition.     

Effect of torsional oscillations on the stress-strain behavior of Al-5 wt% Mg alloy

The microstructure and mechanical properties of a precipitation hardenable Al-5 wt% Mg alloy subjected to low frequency torsional oscillations and aging treatments are reported in the present work. The stress-strain response was examined at different frequencies (1.53-3.3 Hz) and at constant shear strain amplitude (φ = 5.69 × 10⁻⁴). An excessive in the softening was observed by increasing both frequency of the applied oscillations and deformation temperature. The change in the hardening and softening parameters of stress-strain relations was explained in view of spinodal decomposition in Al-Mg systems. The mean value of activation energy was found to be equal to that quoted for precipitate-dislocation intersection.     

Use of a.c. Magnetic Susceptibility for Temperature Measurement and Discrimination Between Spinodal Decomposition and Sigma Phase Formation

Duplex stainless steels are embrittled on exposure to elevated temperatures because of spinodal decomposition (<550°C) and sigma phase formation (between 600°C and 900°C). The sigma phase has been discovered to undergo a paramagnetic-to-ferromagnetic transition at cryogenic temperatures and its Curie temperature has a good dependence on prior annealing temperature. Additionally, it has been found that the room-temperature a.c. magnetic susceptibility also has a good temperature-dependence when spinodal decomposition occurs. It is viable to use room-temperature a.c. magnetic susceptibility and the cryogenic magnetic transition of the sigma phase for 1. temperature measurement and 2. discrimination between spinodal decomposition and sigma phase formation in duplex stainless steels.     

Effects of Zn addition to AuCu on age-hardening behaviors at intraoral temperature

The effect of Zn addition to AuCu on the age-hardening rate at the intraoral temperature was investigated to find out the proper condition for high age-hardening rate. The increase in hardness of Zn-added alloys during aging at 37 °C was due to the atomic ordering. With an increase in Zn concentration, hardness of a sample under the as-quenched condition decreased, but the age-hardening rate obviously increased. When Zn content was fixed, a higher solution treatment temperature was more effective for the age-hardening at 37 °C. It was suggested that the formation energy of a vacancy considerably decreased with an increase in Zn content. It is reasonable to consider that the amount of quenched-in excess vacancies are markedly increased with an increase in Zn content when the solution treatment temperature was fixed. By transmission electron microscopic observations, it was revealed that the formation of the AuCu II superstructure contributed to the age-hardening at 37 °C in the high zinc content alloy.     

THE FRACTURE MECHANISM OF 475°C EMBRITTLEMENT IN A DUPLEX STAINLESS STEEL

The mechanism of “475°C embrittlement” of a duplex stainless steel was investigated using finite element modelling of the stress distribution at brittle fracture initiation. Brittle fracture initiated at a critical shear stress, which increased with ferrite hardness. The fracture stress was affected by the duplex microstructure. Fracture was nucleated by deformation twins, which were identified using electron back-scatter diffraction. The ductile-to-brittle fracture transition was sensitive to age-hardening and could be described simply by the effect of age-hardening and test temperature on the yield stress.     

Effect of phase-separated patterns on the formation of core-shell structure

Revealing the mechanisms of self-organized core-shell(C-S) structure in immiscible systems has drawn considerable attentions, however, the further and fundamental understanding from the point of view of phase-separated pattern remains extremely rare. In this work, by realizing two phase-separated patterns in transparent immiscible system, namely nucleation-growth and spinodal decomposition, their effects on radius of minority-phase droplet(MPD) were examined, and subsequently the effect on C-S structure was further determined. It was found that compared with MPDs produced via nucleation-growth, the MPDs via spinodal decomposition are much larger and easier to form a C-S structure. This is mainly because the larger MPDs can migrate faster and are earlier to reach the sample's center. In addition, two pathways of core formation were observed during the formation of C-S structure: one evolves from a ringlike structure in the phase separation of spinodal decomposition; the other derives from the collision of numerous MPD at sample's center. Such a difference is ascribed to the combination of different growth kinetics and the volume fractions of MPD. These findings might provide an in-depth insight into the C-S structure formation in immiscible systems.     

Decomposition of TiO2-SnO2 solid solutions

Decomposition of TiO₂-SnO₂ solid solutions was studied using large-angle X-ray diffraction, transmission electron microscopy, electron diffraction, and small-angle X-ray scattering. Particular attention was devoted to the initial stages of decomposition of homogeneous solid solutions, so as to determine whether or not decomposition in the system can occur spinodally. All of our results indicate that alloys within the spinodal can decompose by a continuous and spontaneous process, i.e. spinodal decomposition does occur, whereas alloys outside the spinodal decompose by a discontinuous and non-spontaneous process, i.e. decomposition occurs by nucleation and growth.     

Thermodynamically reversible and irreversible control on morphology of multiphase systems

Morphology and properties of polymer alloys can be controlled by thermodynamically reversible (structure freeze-in) or irreversible (structure lock-in) processes via simultaneously manipulating miscibility, mechanisms of phase separation, glass transition (structural relaxation), and cure kinetics of polymer systems. Using phase diagrams consisting of binodal and spinodal curves, the morphology of epoxy/carboxyl-terminated butadiene acrylonitrile copolymer (CTBN) systems can be controlled by the mechanism of nucleation and growth or by spinodal decomposition. We have found that the particle size of the rubber reinforcement in epoxies is affected by the mechanisms of phase separation. Phase separation by nucleation and growth gives larger rubber particles than the corresponding phase separation by spinodal decomposition. This contrast in the morphology development is the consequence of controlling phase separation through chemorheological behaviour. Modification of the phase separation kinetics in epoxy/CTBN systems was extremely effective at altering both morphology and properties of these alloys. This technique offers a means to shift the glass transition temperature of the rubber-rich phase while leaving the glass transition temperature of the epoxy-rich phase intact. Such control over morphology is the key to ultimately controlling material properties.