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Journal Articles

Phase-field mobility for crystal growth rates in undercooled silicates, SiO$$_2$$ and GeO$$_2$$ liquids

Kawaguchi, Munemichi; Uno, Masayoshi*

Journal of Crystal Growth, 585, p.126590_1 - 126590_7, 2022/05

Phase-field mobility, $$L$$, and crystal growth rates in crystallization of 11 oxides or mixed oxides in undercooled silicates, SiO$$_2$$ and GeO$$_2$$ liquids were calculated with a simple phase-field model (PFM), and material dependence of the $$L$$ was discussed. Ratios between experimental crystal growth rates and the PFM simulation with $$L=1$$ were confirmed to be proportional to a power of $$frac{TDelta T}{eta}$$ on the solid/liquid interface process during the crystal growth in a log-log plot. We determined that parameters, $$A$$ and $$B$$, of the $$L=A(frac{k_{B}TDelta T}{6pi^{2}lambda^{3}eta T_{m} })^{B}$$ were $$A=6.7times 10^{-6}$$ to $$2.6$$m$$^4$$J$$^{-1}$$s$$^{-1}$$ and $$B=0.65$$ to $$1.3$$, which were unique for the materials. It was confirmed that our PFM simulation with the determined $$L$$ reproduced quantitively the experimental crystal growth rates. The $$A$$ has a proportional relationship with the diffusion coefficient of a cation molar mass average per unit an oxygen molar mass at $$T_{m}$$ in a log-log graph. The $$B$$ depends on the sum of the cation molar mass per the oxygen molar mass, $$frac{Sigma_{i}M_{i}}{M_{O}}$$, in a compound. In $$frac{Sigma_{i}M_{i}}{M_{O}}leq 25$$, the $$B$$ decreases with the cation molar mass increasing. The assumed cause is that the B represents the degree of the temperature dependence of the $$L$$. Since the cation molar mass is proportional to an inertial resistance of the cation transfer, the $$B$$ decreases with inverse of the cation molar mass. In crystallization of the silicates of heavy cation in $$frac{Sigma_{i}M_{i}}{M_{O}}geq 25$$, the $$B$$ saturates at approximately 0.67, which leads to $$T_{p}approx 0.9T_{m}$$.

Journal Articles

Phase-field model for crystallization in alkali disilicate glasses; Li$$_2$$O-2SiO$$_2$$, Na$$_2$$O-2SiO$$_2$$ and K$$_2$$O-2SiO$$_2$$

Kawaguchi, Munemichi; Uno, Masayoshi*

Journal of the Ceramic Society of Japan, 128(10), p.832 - 838, 2020/10

 Times Cited Count:2 Percentile:16.44(Materials Science, Ceramics)

This study developed phase-field method (PFM) technique in oxide melt system by using a new mobility coefficient ($$L$$). The crystal growth rates ($$v_0$$) obtained by the PFM calculation with the constant $$L$$ were comparable to the thermodynamic driving force in normal growth model. The temperature dependence of the $$L$$ was determined from the experimental crystal growth rates and the $$v_0$$. Using the determined $$L$$, the crystal growth rates ($$v$$) in alkali disilicate glasses, Li$$_2$$O-2SiO$$_2$$, Na$$_2$$O-2SiO$$_2$$ and K$$_2$$O-2SiO$$_2$$ were simulated. The temperature dependence of the $$v$$ was qualitatively and quantitatively so similar that the PFM calculation results demonstrated the validity of the $$L$$. Especially, the $$v$$ obtained by the PFM calculation appeared the rapid increase just below the thermodynamic melting point ($$T_{rm m}$$) and the steep peak at around $$T_{rm m}$$-100 K. Additionally, as the temperature decreased, the $$v$$ apparently approached zero ms$$^-1$$, which is limited by the $$L$$ representing the interface jump process. Furthermore, we implemented the PFM calculation for the variation of the parameter $$B$$ in the $$L$$. As the $$B$$ increased from zero to two, the peak of the $$v$$ became steeper and the peak temperature of the $$v$$ shifted to the high temperature side. The parameters $$A$$ and $$B$$ in the $$L$$ increased exponentially and decreased linearly as the atomic number of the alkali metal increased due to the ionic potential, respectively. This calculation revealed that the $$A$$ and $$B$$ in the $$L$$ were close and reasonable for each other.

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