Influence of water saturation on interlayer properties of HDTMA-, HDTMP-, and HDPy-modified montmorillonite organoclays

Abstract

Surfactant-modified clay minerals, organoclays, are well-studied and used commercially for removing contaminants from water. Nevertheless, dry organoclay properties are typically used to understand and predict contaminant sorption. In this work, the effects of water saturation on two properties important to contaminant sorption were examined: organoclay interlayer space and surfactant alkyl tail conformational ordering. Montmorillonite was modified to 0.25–3.0 CEC using three surfactants: hexadecyltrimethylammonium (HDTMA), hexadecylpyridinium (HDPy), and hexadecyltrimethylphosphonium (HDTMP). At low surfactant-loadings (< 1 CEC and < 15% fOC), water saturation expanded the maximum organoclay interlayer by 4–8 Å, depending on the surfactant and its loading but had little effect on surfactant tail conformational ordering. At low surfactant loadings, water saturation likely promotes contaminant sorption relative to expectations based on dry organoclay properties, particularly for larger contaminants, due to a relaxation of the physical constraints of the interlayer. At higher surfactant loadings, HDTMA and HDTMP organoclays showed relatively small effects of water saturation, but effects were significant for HDPy organoclays. The maximum interlayer space of the HDPy organoclay at 20.7% fOC expanded 3-fold (+22.3 Å) upon hydration, which is attributed to a substantial rearrangement of the pyridinium headgroup. All HDPy organoclays with fOC > 20% experienced a notable increase in the alkyl tail conformational ordering upon hydration, becoming fully solid-like, even as negligible interlayer expansion occurred at the highest loadings. At high HDPy-loading water saturation would likely restrict sorption of contaminants relative to what might be expected based on dry properties, due to the energetic barrier of cavity formation in the more solid-like interlayer phase. This work provides evidence from three types of organoclays that water-saturated organoclay properties can differ substantially from those of dry organoclays. Characterization of organoclays under water-saturated conditions that are relevant to contaminant sorption will facilitate our understanding and improvement of organoclay performance.