# Crystallization Kinetics of an Equimolar Liquid Crystalline Mixture and Its Components
## 3 Results and Discussion  
### Phase Sequence  
The DSC results for MHPOBC, 3F2 HPhF6, and MIX2 HF6 are presented in Figure 2, Figure 3, and Figure 4, respectively. The POM results are shown in Figures S1-S4 in the Supplementary Materials. The DSC curves of MHPOBC collected during cooling (Figure 2a,b) reveal the phase sequence Iso (418.2 K) SmA\({}^{\star}\) (388.3 K) SmC\({}^{\star}\) (386.6 K) SmC\({}_{A}\)\({}^{\star}\) (337.3 K) SmX\({}_{A}\)\({}^{\star}\) (305.3 K) Cr3, where the phase transition temperatures are extrapolated to zero cooling rate. For the cooling rates of 25-40 K/min, the melt crystallization is completed during subsequent heating (Figure 2c,d), and the onset temperature of the cold crystallization is 290-293 K. Upon further heating, another crystal phase or phases appear. For the 6-40 K/min heating rates, there is a Cr3 \(\rightarrow\) Cr2 transition at 319-329 K, which is followed by a Cr2 \(\rightarrow\) Cr1 transition at 336-338 K. For the 2-5 K/min heating rates, there is a direct Cr3 \(\rightarrow\) Cr1 transition at 304-305 K. The phase transition temperatures of MHPOBC, extrapolated to zero heating rate, are Cr3 (317.1 K) Cr1 (351.6 K) SmC\({}_{A}\)\({}^{\star}\) (385.0 K) SmC\({}^{\star}\) (389.3 K) SmA\({}^{\star}\) (416.6 K) Iso. All the transition temperatures are the onset temperatures \(T_{o}\) of anomalies in the DSC thermograms [45], except from the SmC\({}^{\star}\)\(\rightarrow\)SmA\({}^{\star}\) transition, for which the peak temperature \(T_{p}\) was used. Under the polarizing microscope, the MHPOBC sample (Figure S1) shows mainly a fan-shaped texture in SmA\({}^{\star}\) and a broken fan-shaped texture in SmC\({}^{\star}\) and SmC\({}_{A}\)\({}^{\star}\)[30; 31]. In some parts, a homeotropic texture is visible [31]. The areas oriented homeotropically are usually dark, except for the 340-360 K region, where an increase in luminance is observed, with a peak at 349 K. It is explained by a helix inversion, which occurs in this temperature range [46]. SmC\({}^{\star}\) or its sub-phases are not visible in the plot of luminance vs. temperature; the texture collected in 394 K is attributed to them based on visual inspection. In the SmX\({}_{A}\)\({}^{\star}\) phase, the texture is still a broken fan-shaped type, but looks closer to that of the SmA\({}^{\star}\) phase. The decrease in luminance below 305 K indicates crystallization. During heating, the transition between the crystal phases Cr2 and Cr1 shows a broad valley in their luminance in the 317-342 K range. The Cr1 phase melts at 358 K.  
The phase transitions of 3F2 HPhF6 observed in the DSC thermograms during cooling (Figure 3a,b), extrapolated to zero cooling rate, are as follows: Iso (377.6 K) SmC\({}^{\star}\) (365.1 K) SmC\({}_{A}\)\({}^{\star}\) (311.2 K) Cr1. At 2-5 K/min, the sample crystallizes in the phase denoted as Cr1. At 6-10 K/min, a mixture of two crystal phases, Cr1 and Cr2, is formed. At 15-40 K/min, the crystallization to the Cr2 phase is observed. Upon subsequent heating (Figure 3c,d), the cold crystallization of Cr2 from the remaining SmC\({}_{A}\)\({}^{\star}\) phase occurs at 30-40 K/min, with an onset temperature of 291-292 K. A Cr2 \(\rightarrow\) Cr1 transition is observed at 320-321 K, upon heating at 8-40 K/min (for 6 K/min, this anomaly was not visible, due to the small amount of Cr2 formed during cooling). The phase transition temperatures extrapolated to zero heating rate are as follows: Cr1 (325.9 K) SmC\({}_{A}\)\({}^{\star}\) (369.2 K) SmC\({}^{\star}\) (376.9 K) Iso. Under the polarizing microscope, 3F2 HPhF6 shows broken fan-shaped textures in the SmC\({}^{\star}\) and SmC\({}_{A}\)\({}^{\star}\) phases (Figure S2). The SmC\({}^{\star}\)\(\rightarrow\)SmC\({}_{A}\)\({}^{\star}\) transition has a weak impact on luminance during cooling and a significant impact during heating.