ToF-SIMS depth profiling of altered glass

Abstract

Glass and mineral corrosion usually leads to the formation of morphologically and compositionally complex surface layers that can be characterized by various analytical techniques to infer rate control mechanisms. In this study, we investigate the capabilities and limitations of time-of-flight secondary ion mass spectrometry (ToF-SIMS) to better understand chemical processes of glass corrosion. In particular, we focus on the potential impact of the ToF-SIMS ion beam on the distribution of several elements of interest in alteration layers formed on International Simple Glass, a six-oxide reference glass altered in a solution enriched in alkalis and spiked with H 2 18 O. A thin flake of glass partially altered on both sides is analyzed entirely from one side to the other to determine whether atoms weakly bonded to the solid are displaced by the beams. We highlight the beam effect on cations weakly bonded to the silicate network (Li, Na, K, and B, Ca, Cs to a lesser extent) affecting the profile shape of these elements. No impact is observed on 18 O and H, but it is demonstrated that quantification of isotopic ratios is possible only for a limited range of isotopic enrichment.

Insights into the mechanisms controlling the residual corrosion rate of borosilicate glasses

“…Data are normalized to Zr, an immobile element in the gel, and displayed as a function of depth considering the same sputtering rate in the alteration layer and pristine glass. More details are given in recent articles 29,30,62 .…”

Chemical durability of lead crystal glass: Comparison of short‐term aqueous and atmospheric alteration at 90°C

“…The absence of water molecule signal can also be imputed to the ToF‐SIMS vacuum. It has been demonstrated that the vacuum has little effect on water molecule species in altered layers formed in aqueous conditions on borosilicate glass, 47 but it could affect differently lead glass samples altered in aqueous or atmospheric conditions. One way to avoid uncertainty in the future is to use cryogenic preparation of the sample prior to SIMS analysis to avoid water evaporation 47 …”

“…Na is more retained in the AQ altered layer than K, and larger alkalis are known to affect the chemical shift and the quadrupolar coupling of the 27 Al signal of aluminosilicate glasses. 47,65 Both 29 Si and 27 Al NMR results point out that the network has been significantly hydrolyzed and/or dissolved. Yet, the formation of new Q 4 units from lower Q n species by re-condensation or by precipitation, and the overall higher degree of polymerization of the network compared to the pristine glass indicate that the structure has been significantly reorganized following hydrolysis.…”

“…One way to avoid uncertainty in the future is to use cryogenic preparation of the sample prior to SIMS analysis to avoid water evaporation. 47 Full quantitative profiles were calculated from the raw ToF-SIMS data using Equations (2) and (3). The profiles are relatively homogeneous in composition over the thickness of the layer (Figure 1E,F).…”

An Engineered Nanocomposite Copper Coating with Enhanced Antibacterial Efficacy

“…[30,31] XPS and ToF-SIMS analyses did not detect Zn on the surface of NP3, likely because the analysis depths of these techniques are shallow (<10 nm and 1 nm, respectively). [32], [33] In addition, selective leaching of Zn in the presence of Cu is spontaneous and highlyfavourable, since it has a stronger tendency to oxidize than Cu, [34] which also could contribute to our inability to detect Zn using XPS and ToF-SIMS. In contrast, ICP-OES showed progressive Zn ion release from NP3 (Fig.…”