Drying mechanisms in historical egg–oil emulsion binders: a combined ATR-FTIR and unilateral NMR study
Abstract
In the 20th century, painters adopted emulsion-based paints, associating their distinctive rheological and drying properties with the recipes of the Old Masters. These systems dry through a combination of physical and chemical processes, including water evaporation and oxidative cross-linking of unsaturated triglycerides. In this study, we investigate how the composition and structure of oil-in-water (o/w) and water-in-oil (w/o) emulsions affect the drying kinetics and molecular transformations in the resulting paint films, with lead tin yellow as a pigment. Time-resolved ATR-FTIR spectroscopy and low-field NMR relaxometry are combined to monitor both the evaporation of water and the evolution of molecular mobility during cross-linking. We show that the nature of the continuous phase determines the drying pathway: o/w emulsion-based paints initially dry within minutes due to water evaporation, whereas w/o emulsions paints show extended drying times, governed by autoox- idation and polymerization. In emulsions prepared with raw linseed oil, the presence of egg yolk, in the continuous or dispersed phase, significantly delays cross-linking. Conversely, this delay is not observed when lead-treated linseed oil is used suggesting an interaction between lead species and antioxidant compounds in egg yolk. Spatially resolved NMR measurements also reveal the development of molecular mobility gradients across the film thickness when oil is the continuous phase, linked to a gradient in molecular oxygen within the film.
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BibTeX
@article{boullay2026drying,
title = {{Drying mechanisms in historical egg–oil emulsion binders: a combined ATR-FTIR and unilateral NMR study}},
author = {Côme Thillaye Du Boullay and Maguy Jaber and Floriane Gerony and Guillaume Mériguet and Anne-Laure Rollet and Laurence de Viguerie},
journal = {Progress in Organic Coatings},
year = {2026},
month = oct,
doi = {10.1016/j.porgcoat.2025.109735},
url = {https://hal.science/hal-05776967v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Drying mechanisms in historical egg–oil emulsion binders: a combined ATR-FTIR and unilateral NMR study
AU - Côme Thillaye Du Boullay
AU - Maguy Jaber
AU - Floriane Gerony
AU - Guillaume Mériguet
AU - Anne-Laure Rollet
AU - Laurence de Viguerie
PY - 2026
DA - 2026/10/04
JO - Progress in Organic Coatings
DO - 10.1016/j.porgcoat.2025.109735
UR - https://hal.science/hal-05776967v1
AB - In the 20th century, painters adopted emulsion-based paints, associating their distinctive rheological and drying properties with the recipes of the Old Masters. These systems dry through a combination of physical and chemical processes, including water evaporation and oxidative cross-linking of unsaturated triglycerides. In this study, we investigate how the composition and structure of oil-in-water (o/w) and water-in-oil (w/o) emulsions affect the drying kinetics and molecular transformations in the resulting paint films, with lead tin yellow as a pigment. Time-resolved ATR-FTIR spectroscopy and low-field NMR relaxometry are combined to monitor both the evaporation of water and the evolution of molecular mobility during cross-linking. We show that the nature of the continuous phase determines the drying pathway: o/w emulsion-based paints initially dry within minutes due to water evaporation, whereas w/o emulsions paints show extended drying times, governed by autoox- idation and polymerization. In emulsions prepared with raw linseed oil, the presence of egg yolk, in the continuous or dispersed phase, significantly delays cross-linking. Conversely, this delay is not observed when lead-treated linseed oil is used suggesting an interaction between lead species and antioxidant compounds in egg yolk. Spatially resolved NMR measurements also reveal the development of molecular mobility gradients across the film thickness when oil is the continuous phase, linked to a gradient in molecular oxygen within the film.
SN - 0300-9440
ER -