Higler Ruben, Sprakel Joris
Physical Chemistry and Soft Matter, Wageningen University, Wageningen, 6708 WE, The Netherlands.
Sci Rep. 2017 Oct 3;7(1):12634. doi: 10.1038/s41598-017-12730-8.
The addition of a small amount of dopant impurities to crystals is a common method to tune the properties of materials. Usually the doping grade is restricted by the low solubility of the dopants; increasing the doping concentration beyond this solubility limit leads to supersaturated solutions in which dopant clusters dominate the material properties, often leading to deterioration of strength and performance. Descriptions of doped solids often assume that thermal excitations of the on average perfect matrix are small. However, especially for bcc crystals close to their melting point it has recently become clear that the effects of thermal disorder are strong. Here we study the doping of weak bcc crystals of charged colloids via Brownian dynamics simulations. We find a complex phase diagram upon varying the dopant concentration. At low dopant concentrations we find an interstitial solid solution. As we increase the amount of dopants a complex meta-stable liquid-in-solid cluster phase emerges. Ultimately this phase becomes meta-stable with respect to macroscopic crystal-crystal coexistence. These results illustrate the complex behaviour that emerges when thermal excitations of the matrix drive impure crystals to a weak state.
向晶体中添加少量掺杂杂质是调节材料性能的常用方法。通常,掺杂浓度受掺杂剂低溶解度的限制;将掺杂浓度提高到超过该溶解度极限会导致过饱和溶液,其中掺杂剂团簇主导材料性能,常导致强度和性能下降。对掺杂固体的描述通常假设平均完美基质的热激发很小。然而,特别是对于接近熔点的体心立方晶体,最近已清楚地表明热无序效应很强。在此,我们通过布朗动力学模拟研究带电胶体的弱体心立方晶体的掺杂。我们发现改变掺杂剂浓度时会出现复杂的相图。在低掺杂剂浓度下,我们发现一种间隙固溶体。随着掺杂剂数量的增加,会出现一种复杂的亚稳液-固团簇相。最终,相对于宏观的晶体-晶体共存,该相变得亚稳。这些结果说明了当基质的热激发将不纯晶体驱动到弱状态时出现的复杂行为。