Formation and transformation of metastable LPSO building blocks clusters in Mg-Gd-Y-Zn-Zr alloys by spinodal decomposition and heterogeneous nucleation

To study the formation and transformation mechanism of long-period stacked ordered(LPSO)structures,a systematic atomic scale analysis was conducted for the structural evolution of long-period stacked ordered(LPSO)structures in the Mg-Gd-Y-Zn-Zr alloy annealed at 300℃~500℃.Various types of metastable LPSO building block clusters were found to exist in alloy structures at different temperatures,which precipitate during the solidification and homogenization process.The stability of Zn/Y clusters is explained by the first principles of density functional theory.The LPSO structure is distinguished by the arrangement of its different Zn/Y enriched LPSO structural units,which comprises local fcc stacking sequences upon a tightly packed plane.The presence of solute atoms causes local lattice distortion,thereby enabling the rearrangement of Mg atoms in the different configurations in the local lattice,and local HCP-FCC transitions occur between Mg and Zn atoms occupying the nearest neighbor positions.This finding indicates that LPSO structures can generate necessary Schockley partial dislocations on specific slip surfaces,providing direct evidence of the transition from 18R to 14H.Growth of the LPSO,devoid of any defects and non-coherent interfaces,was observed separately from other precipitated phases.As a result,the precipitation sequence of LPSO in the solidification stage was as follows:Zn/Ycluster+Mg layers→various metastable LPSO building block clusters→18R/24R LPSO;whereas the precipitation sequence of LPSO during homogenization treatment was observed to be as follows:18R LPSO→various metastable LPSO building block clusters→14H LPSO.Of these,14H LPSO was found to be the most thermodynamically stable structure.

Effect of Cu on the Spinodal Decomposition of AlZn Alloy with Symmetrical Composition

The effect of Cu addition on the spinodal decomposition of the Al-Zn alloy with symmetrical compositions has been investigated by X-ray diffraction analysis. It is found that the single fcc phase can be obtained in the AlZn alloy with the addition of 2 at. pct Cu after solution treatment at 400℃ and water quenching to room temperature. The modulation structure occurs in two types of alloys aged at room temperature for 30 min. The spinodal process remarkably slows down above or at the three phase equilibrium temperature, particularly at room temperature due to the addition of 2 at. pct Cu. The spinodal time increases by 20 times when aging at 300℃ and by more than 30 times when aging at room temperature.

THE EFFECT OF COLD DEFORMATION ON THE KINETICS OF THE SPINODAL DECOMPOSITION OF Cu-9Ni-6Sn-0.3Ce ALLOY

By means of the measurement of mechnical properties and resistivity and X-ray diffraction and transmission microscopy,the effect of cold deformation on the kinetics of spinodal decomposition of Cu-9Ni-6Sn-0.3Ce alloy was studied.The strengthening process of the cold-worked and aged alloy was found to be accelerated.Using the theory of dislocation,the strengthening in cold-worked alloy can be attributed to the acceleration of spinodal process.

Self-organized layered growth phenomena of diffusion couples with spinodal decomposition in binary alloys

In order to investigate the formation mechanisms of the layered growth phenomena in diffusion couples with spinodal decomposition,a phase field model combined with elastic strain field was employed.Microstructure evolutions of diffusion couple with spinodal decomposition in binary alloys were numerically simulated by considering concentration fluctuation and elastic anisotropy.The simulation results indicate that the number of the periodical layers decreases with the increase of initial concentration fluctuation,even with large elastic anisotropy.The growth of layered microstructures can be attributed to the directional diffusion enhanced by initially discontinuous chemical potential at the interface.

Phase-field study of spinodal decomposition under effect of grain boundary

Grain boundary directed spinodal decomposition has a substantial effect on the microstructure evolution and properties of polycrystalline alloys.The morphological selection mechanism of spinodal decomposition at grain boundaries is a major challenge to reveal,and remains elusive so far.In this work,the effect of grain boundaries on spinodal decomposition is investigated by using the phase-field model.The simulation results indicate that the spinodal morphology at the grain boundary is anisotropic bicontinuous microstructures different from the isotropic continuous microstructures of spinodal decomposition in the bulk phase.Moreover,at grain boundaries with higher energy,the decomposed phases are alternatingα/βlayers that are parallel to the grain boundary.On the contrary,alternatingα/βlayers are perpendicular to the grain boundary.

Microscopic Phase Field Study of the Spinodal Decomposition in Fe-Mo Alloys

The spinodal decomposition in Fe-Mo alloys is studied by microscopic phase field method based on atomic scale.The results show that critical temperature of spinodal decomposition increases with the increment of Mo content,up to a maximum value of 1340 K at the Mo content of 50%.The spinodal decomposition shows a maximum rate at the Mo content of 50% for different Fe-Mo alloys.Comparing with the interconnected microstructure without considering elastic strain energy,the microstructure arrayed alternatively along the elastic soft direction of [01] and [10] is obtained under the effects of elastic strain energy,which will changes into a special 'macrolattice' structure during subsequent coarsening stages.The coarsening of microstructure is restrained by elastic interaction generated by atomic-size difference,and a larger atomic-size difference induces a stronger restraining effect.

THERMODYNAMIC CRITERION OF SPINODAL DECOMPOSITION IN TERNARY SYSTEMS

By expanding the Gibbs free energy of a ternary system into a Taylor series with respect to the composition,a thermodynamic criterion of spinodal decomposition is conducted as G_(xx)(δx)2+2G_(xx)δxδy+G_(yy)(δy)~2<0,from which,various conditions of spinodal decomposition are discussed.When G_(xx)<0 G_(xy)~2-G_(xx)G_(yy)<0,it is called unstable decomposition unrestricted by the direction of composition fluctuation;when G_(xx)<0,G_(xy)~2-G_(xx)G_(yy)>0,or G_(xx)>0, G_(xy)~2-G_(xx)G_(yy)>0,as well as G_(xx)=0,are all considered as unstable decomposition restricted by the direction of composition fluctuation δx and δy.The phenomenon of turning round in composition during spinodal decomposition is attempted to be explained from above point of view.The computer calculated ranges of unstable decomposition according to the criterion of spinodal decomposition on Cu-Ni-Fe ternary system is consistent with the experimental re- sults obtained from literatures.

EFFECT OF Y ON THE SPINODAL DECOMPOSITION RATE AND MECHANICAL PROPERTIES OF Cu-9Ni-6Sn ALLOY

By measurement of mechanical and electrical properties,modulation wavelength,TEM techniques,etc.,the effect of Y on the spinodal decomposition in a Cu-9Ni-6Sn alloy has been studied.The results show that Y can accelerate spinodal decomposition in the alloy,hinder the growth of celluoid structurers occurring at grain boundaries,and improve the combination of strength and plasticity.

Transient spinodal decomposition during annealing of rapidly solidified Al-10Sr alloy

Rapidly solidified Al-10Sr alloy ribbons were prepared using a single roller melt spinning technique. The annealing process of the rapidly solidified Al-10Sr alloy has been carried out using differential scanning calorimetry (DSC). The microstructure of as-annealed Al-10Sr alloy has been characterized by transmission electron microscopy (TEM). The equilibrium AUSr phase is dominant in the as-annealed alloy. Besides the Al4Sr phase, an AlSr phase is also found in the alloy isothermally annealed at 873 K for 90 min. Furthermore, a modulated nanostructure was observed in the alloy isothermally annealed at 873 K for 90 min. With further prolonged annealing time, however, the AlSr phase disappears in the as-annealed alloy. The dependence of particle size and growth rate on annealing time as well as the modulated structure shows that the occurrence of the AlSr phase may be due to the spinodal decomposition.

Achieving high strength and ductility in high-entropy alloys via spinodal decomposition-induced compositional heterogeneity

The compositional heterogeneity in high-entropy alloys(HEAs)has been reported to be an inherent en-tity,which significantly alters the mechanical properties of materials by tuning the variation of lattice resistance for dislocation motion.However,since the body-centered cubic(BCC)structure is not close-packed,the change of lattice resistance is less sensitive to the normal concentration wave compared to that in face-centered cubic(FCC)structured materials.In this work,we selected a refractory bcc HEAs TiZrNbTa for the matrix and added a small amount of Al to facilitate the special spinodal decomposition structure.In particular,(TiZrNbTa)98.5 Al 1.5 displayed a typical basket-weave fabric morphology of spinodal decomposition structure with a characteristic periodicity of∼8 nm and had an optimal combination of strength and ductility(the yield strength of 1123±9 MPa and ductility of∼20.7%±0.6%).It was de-termined that by doing in situ TEM mechanical testing,the plastic deformation was dominated by the formation and operation of dislocation loops which provided both edge and screw components of dislo-cations.The synergetic effect of the remarkable chemical heterogeneity created by the spinodal decompo-sition and the spreading lattice distortion in high entropy alloys is quite effective in tuning the mobility of different types of dislocations and facilitates dislocation interactions,enabling the combination of high strength and ductility.

Phase-field modelling of spinodal decomposition with G-phase precipitation during ageing

The duplex stainless steels(DSSs)are susceptible to thermal ageing embrittlement due to the spinodal decomposition and Gphase precipitation in the ferritic phase.This study presents a ternary(Fe-Cr-Ni)phase-field model for the simulation of spinodal decomposition with concurrent G-phase precipitation.Two Cahn-Hilliard equations and one Ginzburg-Landau equation are used in the model to describe the diffusion of Cr,Ni,and the growth of G-phase,respectively.The model is able to generate a spinodally-interconnected structure with G-phase particles near theα-α′interfaces,similar to experimental observations.The kinetic synergy between spinodal decomposition and G-phase precipitation is discussed.The simulation results indicate that Gphase can enhance the evolution of spinodal decomposition by occupying the volume where the decomposition could otherwise occur,and that the system’s elastic strain energy is largely contributed by G-phase rather than spinodal decomposition.These results would help in better understanding the states of the materials for plant structural integrity assessment and life management.

Ordering-induced Elinvar effect over a wide temperature range in a spinodal decomposition titanium alloy

Temperature-independent elastic modulus is termed as Elinvar effect,which is available by tuning the continuous spin transition of ferromagnetic alloys via composition optimization and the first-order martensitic transformation of shape memory alloys via plastic deformation.However,these reversible mechanisms are restricted generally in a narrow temperature range of less than 300 K.Here reports,by tuning a spinodal decomposition in a Ti-Nb-based titanium alloy via aging treatment,both the Elinvar effect in a wide temperature range of about 500 K and a high strength-to-modulus ratio of about 1.5%can be obtained by a continuous and reversible crystal ordering mechanism.The results demonstrate that the alloy aged at 723 K for 4 h has a nanoscale plate-like modulatedβ+α"two-phase microstructure and its elastic modulus keeps almost constant from 100 to 600 K.Synchrotron and in-situ X-ray diffraction measurements reveal that the crystal ordering parameter of theα"phase increases linearly with temper-ature from 0.88 at 133 K to 0.97 at 523 K but its volume fraction keeps a constant of about 33.8%.This suggests that the continuous ordering of theα"phase toward the high modulusαphase induces a posi-tive modulus-temperature relation to balance the negative relation of the elastically stableβphase.The aged alloy exhibits a high yield strength of 1200 MPa,good ductility of 16%and a high elastic admissible strain of 1.5%.Our results provide a novel strategy to extend the Elinvar temperature range and enhance the strength by tuning the crystal ordering of decomposition alloys.

Formation of Nanometer Coherent Structures During Spinodal Decomposition and Ordering Coexistence Phase Transformation in Fe-24Al Alloys

The nanometer coherent structure evolution of spinodal decomposition and ordering coexistence phase transformation in Fe-24Al alloys is investigated by the microscopic phase field kinetic model.The results show that the concentration and long-range order parameters all continuously change towards to their equilibrium values during phase transformation.With the increase of elastic interaction energy,the anisotropy along [01] or [10] elastic soft direction is more obvious and the time reaching equilibrium state is also shortened.According to the results,the formation of nanometer coherent structures during phase transformation is composed of the initial decreasing stage of order degree stage,the incubation stage,the continuous increasing stage of concentration order parameter and long-range order parameter,and the later stable stage.The spinodal decomposition and ordering is interaction;the initial ordering stage is a necessary condition of the coexistence phase transformation.The nanometer coherent structures are not found to grow during the whole phase transformation.The simulation results are in accordance with the results in experiment obtained by the aging treatment in Fe-24Al alloys.

Effect of composition and aging time on hardness and wear behavior of Cu-Ni-Sn spinodal alloy

Copper alloyed with various compositions of nickel and tin were cast into molds under argon atmosphere.The cast rods were homogenized,solution heat treated,followed by aging for different time duration.The specimens were characterized for microstructure and tested for microhardness and wear rate.A hybrid model with a linear function and radial basis function was developed to analyze the influence of nickel,tin,and aging time on the microhardness and tribological behavior of copper-nickel-sin alloy system.The results indicate that increase in the composition of nickel and tin increases the microhardness and decreases the wear rate of the alloy.The increase in the concentration of nickel and tin decreases the peak aging time of the alloy system.

Influence of quenching medium on the dendrite morphology,hardness,and tribological behaviour of cast Cu-Ni-Sn spinodal alloy for defence application

Cu-Ni-Sn spinodal alloys(Spinodal bronze)are potential materials with robust applications in components associated with defence applications like bearings,propellers,bushes,and shafts of heavily loaded aircraft,off-road vehicles,and warships.This paper presents a comparative study using water,Brine solution,and SAE 40 oil as the quenching media in regular bronze(Cu-6Sn)and spinodal bronze(Cu-9Ni-6Sn)alloys.Morphological analysis was conducted by optical microscopy,transmission electron microscopy(TEM),and X-ray diffraction technique(XRD)on bronze and spinodal bronze samples immersed in the three different quenching media to understand the grain size and hardness values better.Tribological analysis was performed to analyze the effect of quenching media on the wear aspects of bronze and spinodal bronze samples.The hardness value of the brine-aged spinodal bronze samples was as high as 320 Hv,and the grain size was very low in the range of 60μm.A quantitative comparison between brine-aged regular bronze and brine-aged spinodal bronze showed that the hardness(Hv)was almost 80%higher for brine-aged spinodal bronze.Further,the grain size was approximately 30%finer for spinodal bronze when compared with regular bronze.When the load was increased in spinodal bronze samples,there was an initial dip in wear rate followed by a marginal increase.There was a steady increase in friction coefficient with a rise in load for brine-aged regular bronze and spinodal bronze samples.These results indicate that brine solution is the most effective quenching medium for cast Cu-Ni-Sn spinodal alloys.

ON SPINODAL BOUNDARIES OF Al-Li ALLOYS

The spinodal decomposition can occur in Al-Li alloys containing 5.8-14.2 at.% Li at room temperature. The modutated structure wavelength is approximately 3.1 nm for com mercial Al-LI alloys. The limit composition of the miscibility gap is 3.66 -16.06 at.%Li at 298 K. The highest temperature of the miscibility gap is 377 K.

Microstructures of spinodal phases in Cu-15Ni-8Sn alloy

The microstructures of spinodal phases in Cu-15Ni-8Sn alloy were studied by TEM. It was found that when the alloy is completely in a as-quenched state, spinodal decomposition is quick. Ordering appears after spinodal decomposition. The ordered phase with DO22 structure has three variants obtained from coarsening spinodal structure. The reason of ordering appeared after spinodal decomposition is that the content of solute atoms needed by ordering is higher than the average, which can be reached by the composition fluctuation of spinodal decomposition. It was speculated that the morphology of the ordered phase is needle-like.

Thermal Induced Periodic Phase Separation in Polymer Blends

Simulations were carried out for studying the periodic phase separation of a symmetric binary polymer blend on the basis of Cahn-Hilliard-Cook theory. The time dependent interaction parameter x（τ） was assumed to undergo a step-wise oscillation. The hierarchic structures composed of both large and small domains were obtained. The mechanism of the periodic formation of hierarchic structures was also demonstrated.

Age-hardening behavior and microstructure of Cu-15Ni-8Sn-0.3Nb alloy prepared by powder metallurgy and hot extrusion

Cu-15Ni-8Sn-0.3Nb alloy rods were prepared by means of powder metallurgy followed by hot extrusion.Element maps obtained by electron probe micro analyzer(EPMA)showed that Nb-rich phases were formed and distributed within grains and at grain boundaries of the Cu-15Ni-8Sn-0.3Nb alloy.Transmission electron microscope(TEM)results indicated that there was no obvious orientation relationship between these phases and the matrix.Spinodal decomposition and ordering transformation appeared at early stages of aging at400°C and caused significant strengthening.Cu-15Ni-8Sn-0.3Nb alloy exhibited both higher strength(ultimate tensile strength>1030MPa)and higher tensile ductility(elongation>9.1%)than Cu-15Ni-8Sn alloy after aging treatment.The improvement was caused by Nb-rich phases at grain boundaries which led o the refinement of grain size and postponed the growth of discontinuous precipitates during aging.

Microstructural Changes of Cu-Ni-Si Alloy during Aging

Age hardening in Cu-3.2Ni-0.75Si (wt pct) and Cu-1.0Ni-0.25Si (wt pct) alloys from 723 to 823 K is studied. After an incubation period strengthening appears which is due to precipitates in the Cu-l.ONi-0.25Si (wt pct) alloy. On other hand an immediate increase of the yield strength characterizes the aging of the alloy. This is followed by the regions of constant yield strength and further by a peak. The microstructure of the alloy was studied by, means of transmission electron microscope (TEM) and X-ray diffraction (XRD). Spinodal decomposition takes place followed by nucleation of the ordering coherent (Cu,Ni)3Si particles, further precipitation annealing coherent δ-Ni2Si nucleated within the (Cu,Ni)3Si particle. Any change of the yield strength can be described by an adequate change of the structure in the sample. The nature of the aging curves with a 'plateau' is discussed. The formulas of Ashby and Labusch can be used to explain the precipitation.