Dimer fatty acid-based polyamide/organoclays : structural, thermal properties, and statistical analysis of factors affecting polymer chain intercalation in bentonite layers

Abstract

This work investigates the potential industrial applications of two sodium bentonite samples (white and yellow), obtained from raw Ca-rich bentonite from Maputo Province in Southern Mozambique. Bentonite bio-organoclays were successfully developed from two Mozambican montmorillonite clays through the intercalation of protonated dimer fatty acid-based polyamide chains using a solution casting method. X-ray diffraction (XRD) analysis confirmed polymer intercalation, with the basal spacing (d001) increasing from approximately 1.5 nm to 1.7 nm as the polymer concentration varied between 2.5 and 7.5 wt.%. However, the extent of intercalation was limited at this stage, suggesting that polymer concentration alone had a minimal effect, likely due to the formation of agglomerates. In a subsequent optimization phase, the influence of temperature (30–90 °C), stirring speed (1000–2000 rpm), and contact time (30–90 min) was evaluated while maintaining a constant polymer concentration. These parameters significantly enhanced intercalation, achieving d001 values up to 4 nm. Statistical Design of Experiments and Response Surface Methodology revealed that temperature and stirring speed exerted a stronger influence on d001 expansion than contact time. Optimal intercalation occurred at 90 °C, 1500 rpm, and 60 min. The predictive models demonstrated high accuracy, with R2 values of 0.9861 for white bentonite (WB) and 0.9823 for yellow bentonite (YB). From statistical modeling, several key observations emerged. Higher stirring speeds promoted intercalation by enhancing mass transfer and dispersion; increased agitation disrupted stagnant layers surrounding the clay particles, facilitating deeper penetration of the polymer chains into the interlayer galleries and preventing particle settling. Furthermore, the ANOVA results showed that all individual and interaction effects of the factors investigated had a significant influence on the d001 spacing for both WB and YB clays. Each factor exhibited a positive effect on the degree of intercalation.