ABSTRACT
Using the recently developed techniques of electron tomography, we have explored the first stages of disfiguring formation of zinc soaps in modern oil paintings. The formation of complexes of zinc ions with fatty acids in paint layers is a major threat to the stability and appearance of many late 19th and early 20th century oil paintings. Moreover, the occurrence of zinc soaps in oil paintings leading to defects is disturbingly common, but the chemical reactions and migration mechanisms leading to large zinc soap aggregates or zones remain poorly understood. State-of-the-art scanning (SEM) and transmission (TEM) electron microscopy techniques, primarily developed for biological specimens, have enabled us to visualize the earliest stages of crystalline zinc soap growth in a reconstructed zinc white (ZnO) oil paint sample. In situ sectioning techniques and sequential imaging within the SEM allowed three-dimensional tomographic reconstruction of sample morphology. Improvements in the detection and discrimination of backscattered electrons enabled us to identify local precipitation processes with small atomic number contrast. The SEM images were correlated to low-dose and high-sensitivity TEM images, with high-resolution tomography providing unprecedented insight into the structure of nucleating zinc soaps at the molecular level. The correlative approach applied here to study phase separation, and crystallization processes specific to a problem in art conservation creates possibilities for visualization of phase formation in a wide range of soft materials.
ABSTRACT
Zinc oxide is a prevalent industrial-age pigment that readily reacts with fatty acids in oil-based paints to form zinc carboxylates. Zinc stearate aggregates are associated with deterioration in late nineteenth and twentieth century paintings. The current study uses both conventional and synchrotron Fourier transform infrared spectroscopy (FT-IR) to investigate metal carboxylate composition in a range of naturally aged artists' oil paints and reference paint film draw-downs. The paints contain zinc oxide alone or in combination with lead white, titanium white, and aluminum stearate and are prepared with linseed and safflower oils. Attenuated total reflectance (ATR)-FT-IR using the conventional source identifies marked differences in carboxylate profiles between exposed and protected surfaces in a large number of samples. Synchrotron FT-IR microspectroscopy of thin paint cross-sections maps metal carboxylate distributions at high spatial resolution and resolves broad concentration gradients and micrometer-scale phase separation of carboxylate species. Aluminum stearate, a common paint additive, is found to influence the distribution of zinc carboxylates more strongly than pigment composition or oil type. The presence of aluminum stearate results in higher concentrations and more pronounced separation of saturated C16 and C18 chain zinc carboxylates in the margin of paint nearest the polyester substrate. The presence of aluminum stearate in association with zinc oxide has a clear influence on zinc carboxylate formation and distribution, with potential implications for long term stability of vulnerable paintings.
