Electronic Supplementary Information for Chem. Soc. Rev. paper.

1. 1 Heterogeneous nucleation of/on nanoparticles: a density functional study using the phase-field crystal model (Animations for Figs. 9, 10, 11, 14, 16 & 18 and for pure Fe) L. Gránásy1,2, F. Podmaniczky, G. I. Tóth1, G. Tegze, & T. Pusztai1 1Wigner Research Centre for Physics, POB 49, H-1525 Budapest, HU 2BCAST, Brunel University, Uxbridge, Middlesex, UB8 3PH, UK Electronic Supplementary Information for Chem. Soc. Rev. paper. Ppt file downloadable from: http://www.szfki.hu/~grana/rsc_review/Elect_Suppl_Info.ppt

2. Zhang & Liu, JACS (2007) A. Nucleation ( = 1, single mode-PFC)  = 0.1684 0 = 0.25 Red (bcc-like) if q4  [0.02, 0.07] q6  [0.48, 0.52] 256256256 grid Tóth et al.PRL (2011). req= 0.1330 Fig. 9 Starts to solidify as amorphous, then crystallizes! A’la 2D & 3D colloids. Steinhardt, Nelson, Ronchetti, PRB (1983) 2 Please read comment to the slide

3. qi of Lechner & Dellago qi of Steinhardt et al. B. Structural evolution: Black: bcc Yellow: Icosah. Green: hcp Red: fcc Red (bcc-like) if q4  [0.02, 0.07] q6  [0.48, 0.52] Medium Range Crystalline Order (MRCO) Greenq6 > 0.4 Redq6 [0.28, 0.4] Whiteq6 < 0.28 Kawasaki & Tanaka, PNAS (2010) • Observations: • - PFC does not see MRCO of Kawasaki & Tanaka • - Some grain boundaries are “amorphous” • Am. precursor is structurally like LJ liquid • - Heterogeneous bcc nucleation on am. surfaces Solid bond no.:  Pink: low Blue: high 3 Figs. 9, 10, 11 Please read comment to the slide 14

4. Further structural analysis: 4 Fig. 9 Solid bond no.:  Pink: low Blue: high Solid bond number, :

5. n0 = 0.5125 T = Tf Advanced PFC for Fe: 5 300300300 grid n0 = 0.52 MD am. Fe:Hong, Nanotech. (2009) n0 = 0.55 The appearance of an amorphous precursor prior to crystal nucleation might be fairly general. Please read comment to the slide

6. (Greeret al., Acta Mater., 2002) T = 17 K d = 30 nm T = 18 K Horizontal: 1 = 75 Vertical: 2 = 175 40 nm  40 nm  40 nm 6 B. Particle induced freezing in 2D and 3D (solving the Euler-Lagrange equation): - Cylindrical particles ~ wet by the crystal on top/bottom, not on sides; (e.g., Al + Al-Ti-B inoculant  Ti2B particles with AlTi3 coating on {0001} faces different contact angles on different faces) - Free growth for - PFT simulations  Tc  1/d; Tc < classical Please read comment to the slide

7.  = 0.5 as/ = 1.0  = 0.25 7 Single mode PFC modeling of nanoparticle induced crystallization in 2D: (results obtained by solving the Euler-Lagrange equation) EL solutions for increasing driving force: as/ = 1.0 Results: - Small anisotropy: Greer’s model OK - Faceted: free-growth at a much larger driving force Fig. 14 Homogeneous nuclei at the critical driving force Tóth et al.PRL (2012). Please read comment to the slide

8. 8 Single mode PFC of particle induced freezing in 3D (solving the Euler-Lagrange equation):  = 0.25 SC substrate Cubic shape 512  512  512 grid Please read comment to the slide Fig. 16 256  256  256 grid Tóth et al.PRL (2012).

9.  = 0.25 0 = 0.32  = 0.1 as/ = 1.39 Heterogeneous crystal nucleation in 2D (solving Equation of Motion): 9 Fig. 18 Realization: - Square lattice (periodic potential) - Noise represents thermal fluctuations. Observation: - Heterogeneous crystal nucleation - Capillary waves on the crystal-liquid front Please read comment to the slide