X-ray photoelectron spectroscopic investigation of nanocrystalline calcium silicate hydrates synthesised by reactive milling

X-ray photoelectron spectroscopy (XPS) has been used to analyse a series of mechanochemically synthesised, nanocrystalline calcium silicate hydrates (C-S-H). The samples, with Ca/Si ratios of 0.2 to 1.5, showed structural features of C-S-H(I). XPS analysis revealed changes in the extent of silicate polymerisation. Si 2p, Ca 2p and O 1s spectra showed that, unlike for the crystalline calcium silicate hydrate phases studied previously, there was no evidence of silicate sheets (Q3) at low Ca/Si ratios. Si 2p and O 1s spectra indicated silicate depolymerisation, expressed by decreasing silicate chain length, with increasing C/S. In all spectra, peak narrowing was observed with increasing Ca/Si, indicating increased structural ordering. The rapid changes of the slope of FWHM of Si 2p, ΔCa–Si and ΔNBO–BO as function of C/S ratio indicated a possible miscibility gap in the C-S-H-solid solution series between C/S 5/6 and 1. The modified Auger parameter (α′) of nanocrystalline C-S-H decreased with increasing silicate polymerisation, a trend already observed studying crystalline C-S-H. Absolute values of α′ were shifted about − 0.7 eV with respect to crystalline phases of equal C/S ratio, due to reduced crystallinity.