In Situ Soft X-ray Spectromicroscopy of Early Tricalcium Silicate Hydration.

The understanding and control of early hydration of tricalcium silicate (C₃S) is of great importance to cement science and concrete technology. However, traditional characterization methods are incapable of providing morphological and spectroscopic information about in situ hydration at the nanoscale. Using soft X-ray spectromicroscopy, we report the changes in morphology and molecular structure of C₃S at an early stage of hydration. In situ C₃S hydration in a wet cell, beginning with induction (1 h) and acceleration (4 h) periods of up to ~8 h, was studied and compared with ex situ measurements in the deceleration period after 15 h of curing. Analysis of the near-edge X-ray absorption fine structure showed that the Ca binding energy and energy splitting of C₃S changed rapidly in the early age of hydration and exhibited values similar to calcium silicate hydrate (C-S-H). The formation of C-S-H nanoseeds in the C₃S solution and the development of a fibrillar C-S-H morphology on the C₃S surface were visualized. Following this, silicate polymerization accompanied by C-S-H precipitation produced chemical shifts in the peaks of the main Si K edge and in multiple scattering. However, the silicate polymerization process did not significantly affect the Ca binding energy of C-S-H.