The Mixing Enthalpy of the Ternary (Pb, Sn, Zn) Liquid Phase - Calorimetric Measurements and Modelling Outside and Inside the Miscibility Gap

Author(s):  
Abdelhamid Bourkba ◽  
Jean-Marc Fiorani ◽  
Christophe Naguet ◽  
Jean Hertz
Entropy ◽  
2018 ◽  
Vol 20 (11) ◽  
pp. 890 ◽  
Author(s):  
Nicholas Derimow ◽  
Reza Abbaschian

It has been 14 years since the discovery of the high-entropy alloys (HEAs), an idea of alloying which has reinvigorated materials scientists to explore unconventional alloy compositions and multicomponent alloy systems. Many authors have referred to these alloys as multi-principal element alloys (MPEAs) or complex concentrated alloys (CCAs) in order to place less restrictions on what constitutes an HEA. Regardless of classification, the research is rooted in the exploration of structure-properties and processing relations in these multicomponent alloys with the aim to surpass the physical properties of conventional materials. More recent studies show that some of these alloys undergo liquid phase separation, a phenomenon largely dictated by low entropy of mixing and positive mixing enthalpy. Studies posit that positive mixing enthalpy of the binary and ternary components contribute substantially to the formation of liquid miscibility gaps. The objective of this review is to bring forth and summarize the findings of the experiments which detail liquid phase separation (LPS) in HEAs, MPEAs, and CCAs and to draw parallels between HEAs and the conventional alloy systems which undergo liquid-liquid separation. Positive mixing enthalpy if not compensated by the entropy of mixing will lead to liquid phase separation. It appears that Co, Ni, and Ti promote miscibility in HEAs/CCAs/MPEAs while Cr, V, and Nb will raise the miscibility gap temperature and increase LPS. Moreover, addition of appropriate amounts of Ni to CoCrCu eliminates immiscibility, such as in cases of dendritically solidifying CoCrCuNi, CoCrCuFeNi, and CoCrCuMnNi.


1978 ◽  
Vol 125 (7) ◽  
pp. 1053-1058 ◽  
Author(s):  
R. E. Nahory ◽  
M. A. Pollack ◽  
E. D. Beebe ◽  
J. C. DeWinter ◽  
M. Ilegems

2010 ◽  
Vol 10 (16) ◽  
pp. 7795-7820 ◽  
Author(s):  
A. Zuend ◽  
C. Marcolli ◽  
T. Peter ◽  
J. H. Seinfeld

Abstract. Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, Cj*, by including water and other inorganics in the absorbing phase. Such a Cj* definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.


Materials ◽  
2020 ◽  
Vol 13 (22) ◽  
pp. 5268
Author(s):  
Takeshi Nagase

The Ti–Ag alloy system is an important constituent of dental casting materials and metallic biomaterials with antibacterial functions. The binary Ti–Ag alloy system is characterized by flat liquidus lines with metastable liquid miscibility gaps in the phase diagram. The ternary Ti–Ag-based alloys with liquid phase separation (LPS) were designed based on the mixing enthalpy parameters, thermodynamic calculations using FactSage and Scientific Group Thermodata Europe (SGTE) database, and the predicted ground state diagrams constructed by the Materials Project. The LPS behavior in the ternary Ti–Ag–Nb alloy was investigated using the solidification microstructure analysis in arc-melted ingots and rapidly solidified melt-spun ribbons via trans-scale observations, combined with optical microscopy (OM), scanning electron microscopy (SEM) including electron probe micro analysis (EPMA), transmission electron microscopy (TEM), and scanning transmission electron microscopy (STEM). The solidification microstructures depended on the solidification processing in ternary Ti–Ag–Nb alloys; macroscopic phase-separated structures were observed in the arc-melted ingots, whereas fine Ag globules embedded in the Ti-based matrix were observed in the melt-spun ribbons.


2011 ◽  
Vol 9 (1) ◽  
pp. 149-156 ◽  
Author(s):  
Nikolina Milcheva ◽  
Jolanta Romanowska ◽  
Gueorgui Vassilev

AbstractExperimental data of bismuth activity coefficients at 1773 K were obtained by isopiestic method and compared to calculated values. Thermodynamic properties of the Sn-Ni-Bi liquid phase were estimated by means of the general solution model and by the methods of Kohler. Description of the ternary liquid phase (Gibbs excess energy dependence on the temperature and the composition) was achieved by using available thermodynamic data of the constitutive binary systems (Ni-Bi, Sn-Bi, Sn-Ni). A comparison between calculated quantities and experimental data wasconducted. The present assessment with thermodynamically optimized values of the system Sn-Ni-Bi (obtained by the CALPHAD approach) was in good agreement. The suggested appearance of a liquid phase miscibility gap at high temperatures is in agreement with the experimental bismuth activity data and with the assessed thermochemical functions.


2016 ◽  
Vol 879 ◽  
pp. 2439-2443 ◽  
Author(s):  
Qian Sun ◽  
Hong Xiang Jiang ◽  
Jiu Zhou Zhao

Experiments were carried to investigate the effect of TiC on the solidification process and microstructure of Al-Pb alloys. It is demonstrated that TiC particles are effective inoculants for the nucleation of the Pb-rich droplets during cooling an Al-Pb alloy in the miscibility gap. A model describing the kinetic behavior of TiC particles in the melt and the liquid-liquid decomposition of Al-Pb was developed. The dissolution, coarsening and precipitation processes of TiC particles as well as the microstructure evolution during the liquid-liquid phase transformation of an Al-Pb alloy were calculated. The numerical results indicate that what determines the refinement efficiency of TiC particles on the Pb-rich droplets/particles is the number density of TiC particles in the melt cooled to the binodal line temperature of the Al-Pb alloy. If the number density of TiC particles in the melt before the beginning of the liquid-liquid decomposition is high enough, the addition of TiC causes a refinement of the Pb-rich droplets/particles and promotes the formation of Al-Pb alloys with a well dispersed microstructure.


1991 ◽  
Vol 9 (1-3) ◽  
pp. 125-128 ◽  
Author(s):  
J.-L. Lazzari ◽  
E. Tournié ◽  
F. Pitard ◽  
A. Joullié ◽  
B. Lambert

2020 ◽  
Vol 993 ◽  
pp. 39-44
Author(s):  
Xiao Jun Sun ◽  
Jie He ◽  
Jiu Zhou Zhao

The binary Cu-Fe system is characterized by a metastable liquid miscibility gap. WhenZr is added into the Cu-Fe alloy, the miscibility gap can be extended into Cu-Fe-Zr ternary system. In the present study Cu-Fe-Zr alloys were prepared by single-roller melting-spinning method, and the samples were characterized by the SEM, EDS, HRTEM and nanoidentation. The results show that liquid-liquid phase separation into CuZr-rich and FeZr-rich liquids takes place during rapid cooling the Cu-Fe-Zr alloy, and the mechanism depends on the atomic ratio of Cu to Fe. With increasing Zr content, the size of secondary phase formed by the liquid-liquid phase separation reduces to nanoscale. The structure with amorphous Cu-rich nanoparticles embedded in the amorphous Fe-rich matrix was obtained in the as-quenched Cu20Fe20Zr60 alloy. For its structure particularity of the Cu20Fe20Zr60 sample, mechanical evaluation was carried out by using nanoindentation.


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