Kang Jeongki, Kim Jinsoo, Kim Woo-Sik
Functional Crystallization Center, Department of Chemical Engineering (Integrated Engineering Program), Kyung Hee University, Yong-in, Gyeonggi-do 17104, South Korea.
Process Research Department, Research & Development Division, Yuhan Corporation, Yong-in, Gyeonggi-do 17084, South Korea.
ACS Omega. 2023 May 4;8(19):17116-17121. doi: 10.1021/acsomega.3c01435. eCollection 2023 May 16.
Glycine had three polymorphs, two metastable phases (α-glycine, β-glycine) and one stable phase (γ-glycine). However, the phase transformation of glycine from α-phase to γ-phase was well known as the kinetically unfavorable process. In this study, a simple and effective grinding method for phase transformation of glycine from α-phase to γ-phase is proposed. In an aqueous solution, α-glycine and γ-glycine had bulk solubilities of 180 and ∼172 g/L, respectively. According to the Ostwald-Freundlich equation, however, as the crystal size of α-glycine was reduced to ∼0.6 μm by grinding, the saturated concentration of α-glycine increased from 180 to 191 g/L. As long as the solution concentration exceeds a critical point (σ = 0.1), it can be possible to suddenly induce the nucleation of γ-glycine by grinding the α-glycine crystal in the solution. Subsequently, the complete transformation of α-phase to γ-phase was achieved without additives. Similarly, the grinding method was effective for producing the γ-glycine crystal in the cooling crystallization whereas the α-glycine crystal was always produced in the cooling crystallization without grinding. This study showed that physical grinding can effectively facilitate phase transformation by triggering the nucleation of stable polymorph.
甘氨酸有三种多晶型物,两种亚稳相(α-甘氨酸、β-甘氨酸)和一种稳定相(γ-甘氨酸)。然而,甘氨酸从α相到γ相的相变是众所周知的动力学不利过程。在本研究中,提出了一种将甘氨酸从α相转变为γ相的简单有效的研磨方法。在水溶液中,α-甘氨酸和γ-甘氨酸的本体溶解度分别为180和172 g/L。然而,根据奥斯特瓦尔德-弗伦德里希方程,通过研磨将α-甘氨酸的晶体尺寸减小至0.6μm时,α-甘氨酸的饱和浓度从180 g/L增加到191 g/L。只要溶液浓度超过临界点(σ = 0.1),通过在溶液中研磨α-甘氨酸晶体就有可能突然诱导γ-甘氨酸的成核。随后,在无添加剂的情况下实现了从α相到γ相的完全转变。同样,研磨方法在冷却结晶中对于生成γ-甘氨酸晶体是有效的,而在未研磨的冷却结晶中总是生成α-甘氨酸晶体。本研究表明,物理研磨可以通过触发稳定多晶型物的成核有效地促进相变。