Characterization of Nanoparticles in Ethanolic Suspension Using Single Particle Inductively Coupled Plasma Mass Spectrometry: Application for Cementitious Systems

Abstract

Single particle inductively coupled plasma mass spectrometry (spICP-MS) is a well-established technique to characterize the size, particle number concentration (PNC), and elemental composition of engineered nanoparticles (NPs) and colloids in aqueous suspensions. However, a method capable of directly analyzing water-sensitive or highly reactive NPs in alcoholic suspension has not been reported yet. Here, we present a novel spICP-MS method for characterizing the main cement hydration product, i.e., calcium-silicate-hydrate (C-S-H) NPs, in ethanolic suspensions, responsible for cement strength. The method viability was tested on a wide range of NP compositions and sizes (i.e., from Au, SiO₂, and Fe₃O₄ NP certified reference materials (CRMs) to synthetic C-S-H phases with known Ca/Si ratios and industrial cement hardening accelerators, X-Seed 100/500). Method validation includes comparisons to nanoparticle tracking analysis (NTA) and transmission/scanning electron microscopy (TEM/SEM). Results show that size distributions from spICP-MS were in good agreement with TEM and NTA for CRMs ≥ 51 nm and the synthetic C-S-H phases. The X-Seed samples showed significant differences in NP sizes depending on the elemental composition, i.e. CaO and SiO₂ NPs were bigger than Al₂O₃ NPs. PNC via spICP-MS was successfully validated with an accuracy of 1 order of magnitude for CRMs and C-S-H phases. The spICP-MS Ca/Si ratios matched known ratios from synthetic C-S-H phases (0.6, 0.8, and 1.0). Overall, our method is applicable for the direct and element-specific quantification of fast nucleation and/or mineral formation processes characterizing NPs (ca. 50–1000 nm) in alcoholic suspensions.