Atomic scale structural analysis of liquid immiscibility in binary silicate melt: A case of SiO2‒TiO2 system

doi:10.1016/j.jmst.2020.03.035

Abstract

Abstract:

Thermodynamic/dynamic modeling of liquid immiscibility in silicates is seriously hindered due to lack of in situ investigation on the structural evolution of the melt. In this work, atomic-scale structural evolution of a classic binary silicate immiscible system, SiO₂-TiO₂, is tracked by in situ high energy X-ray diffraction (HE-XRD). It is found that both the configuration of [SiO] and the polymerization between them are closely coupled with embedment and extraction of the metallic cations (Ti⁴⁺). [SiO] monomer goes through deficit-oxygen and excess-polymerization before liquid?liquid separation and enables self-healing after liquid?liquid separation, which challenges the traditional cognition that [SiO₄] monomer is immutable. Ti⁴⁺ cations with tetrahedral oxygen-coordination first participate in the network construction before liquid separation. The four-fold Ti-O bond is broken during liquid separation, which may facilitate the movement of Ti⁴⁺ across the Si-O network to form TiO₂-rich nodules. The structural features of nodules were also investigated and they were found highly analogous to that of molten TiO₂, which implies a parallel crystallization behavior in the two circumstances. Our results shed light on the structural evolution scenario in liquid immiscibility at atomic scale, which will contribute to constructing a complete thermodynamic/dynamic framework describing the silicate liquid immiscibility systems beyond current models.

Key words: Liquid immiscibility, Atomic scale structure, Synchrotron radiation, In-situ HE-XRD, SiO₂-TiO₂ melt

Cuiyu Zhang, Xuan Ge, Qiaodan Hu, Fan Yang, Pingsheng Lai, Caijuan Shi, Wenquan Lu, Jianguo Li. Atomic scale structural analysis of liquid immiscibility in binary silicate melt: A case of SiO₂‒TiO₂ system[J]. J. Mater. Sci. Technol., 2020, 53: 53-60.

Figures/Tables 5

Fig. 1. (a) Equilibrium phase diagram of the SiO2-TiO2 binary system [26]. The two compositions and the selected temperatures for investigation are indicated by the arrows in the figure. The top-left inset figure is the SEM image of the SiO2-rich composition (70SiO2?30TiO2) after liquid immiscibility and quenching to room temperature, and the colored figure below is the associated EDS mapping of the selected area. SEM and EDS show that spherical TiO2-rich nodules are dispersed in the SiO2-rich matrix with sharp interfaces, indicating a nucleation-growth liquid-liquid separation mechanism. (b) Schematic diagram of the temperature-time profile in the diffraction experiment. The inset figure illustrates the aerodynamic levitation setup equipped with in-situ HEXRD.

Fig. 2. (a) Fiber-Ziman structure factors S(Q) of the 70SiO2?30TiO2 melt at different temperatures. (b) The pair distribution functions g(r) obtained by Fourier transform of the structure factors. (c) The total distribution functions T(r) derived by g(r): $T(r)=4\text{ }\!\!\pi\!\!\text{ }{{\rho }_{0}}rg(r)$. (d) The calculated weighting factors Wij of each atomic pair in this rich-SiO2 melt contributing to the total X-ray scattering intensity.

Table 1 The statistically average structure parameters of cation-oxygen and cation?cation pairs in the 70SiO2-30TiO2 melt. These data were calculated based on the peaks splitting and fitting results shown in Fig. 2(c).

Temperature	Si-O CN	Ti-O BL (?)	Ti-O CN	Si-Si BL (?)	Si-Si CN	Ti-Ti BL (?)	Ti-Ti CN
2493 K	3.25	1.87	4.59	2.92	5.99	3.61	7.41
2223 K	3.67	1.86	4.23	2.90	5.50	3.59	7.71
1873 K	3.62	1.86	5.47	2.85	4.00	3.68	8.55

Fig. 3. (a) The Fiber-Ziman structure factors S(Q) of the 8.33SiO2-91.67TiO2 melt at different temperatures. S(Q) for pure TiO2 adopted from Alderman et al. [33] is also plotted for comparison. (b) The calculated weighting factors Wij of each atomic pair in this TiO2-rich melt. The contribution of Si?Si is extremely low and thus not shown here. (c) The temperature dependence of total distribution functions. (d) Dependence of the quality-of-fit parameter Rχ on the upper cutoff distance rk, max for the TiO2-rich melt at the three selected temperatures.

Fig. 4. Schematic diagrams of the structural evolution during liquid immiscibility: (a) Homogeneous liquid separates into heterogeneous phases when it is cooled below the binodal dome; (b) the structure evolution of the TiO2-rich nodules from stable to metastable state.

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Atomic scale structural analysis of liquid immiscibility in binary silicate melt: A case of SiO₂‒TiO₂ system

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