ABSTRACT
In a cultural heritage context, fatty acids are usually found as breakdown products of lipid-containing organic remains in archaeological findings, binders in aged oil paintings, and additives in modern art-related materials. They may further interact with the ionic environment transforming into metal soaps, a process that has been recognized as a threat in aged paintings but has received less attention in archaeological objects. The investigation of the above related categories of materials with infrared spectroscopy can provide an overall picture of the organic components' identity and demonstrate their condition and prehistory. The capability of investigating and distinguishing fatty acids and their metal soaps through their rich infrared features, such as the acidic carbonyl, the carboxylate shifts, the variable splits of alkyl chain stretching, bending, twisting, wagging, and rocking vibrations, as well as the hydroxyl peak envelopes and acid dimer bands, allows for their direct detailed characterization. This paper reviews the infrared spectra of selected saturated fatty monoacids and diacids, and their corresponding sodium, calcium, and zinc salts and, supported by newly recorded data, highlights the significance of their spectroscopic features.
ABSTRACT
The question for discriminating iron gall inks is addressed by correlating their infrared (IR) spectra in liquid and dried states with the materials used in their formulations and considering their possible interactions. A series of laboratory inks were prepared according to historic recipes, mainly found in 19th-century documents, and were accordingly studied using Fourier transform infrared (FT-IR) spectroscopy. All ink formulations were based on Aleppo galls, ferrous sulfate, and gum arabic at variable proportions, with various added components, such as alum, vinegar, glycerol, sugar, silver nitrate, cloves, and white wine. Ingredients of the corresponding inks were recognized by means of their IR fingerprints in both their liquid and dried states, respectively. Although a few inks of distinct formulations showed discernible differences in their spectra, the majority showed quite similar absorptions. Principal component analysis and discriminant analysis were employed to successfully discriminate inks, based on their IR peaks. Spectra recorded in the liquid state, despite their broad absorption features, led to satisfactory discrimination of certain types of inks as most of their ingredients are reflected in their IR peaks. Spectra from dried inks contained similar information, which equally worked in a sufficient discriminatory way. Key IR peaks in the recorded spectra of inks made with the addition of special ingredients, such as vinegar, wine, alum, glycerol, and sugar, as well as those prepared with specific tannin-enhancing procedures, such as gall boiling, were located and used in the discrimination basis.
ABSTRACT
An ethylene-methacrylic acid copolymer, formulated by BASF as a waterborne suspension of its alkylammonium salt and used, among other applications, in art conservation as a temporary protective coating was characterized using Fourier transform infrared (FT-IR) spectroscopy aided by modulated differential scanning calorimetry (MDSC) and ellipsometry. The thermal conversion of thin copolymer films from the freshly applied state, where carboxylic acid and carboxylate ion functional groups co-exist, to a purely acidic working state was spectroscopically followed. Transmission mid-infrared data of the working state showed a 1 : 12 ratio of methacrylic acid towards ethylene units. The glass transition temperature (T(g)) in the same state was found at 45 °C. Copolymer films spin-coated on mechanically polished bronze and iron coupons were characterized with transflection infrared spectroscopy and compared to corresponding transmission mid-infrared spectra of copolymer films spin-coated on silicon wafers. In the case of bronze coupons, evidence for interaction of the carboxylate ion with the copper substrate was obtained. The chemical structure and the thermal behavior of the coating, as well as some implications on its protective capability towards iron and copper alloys, is discussed as this material has received considerable attention in the field of metal conservation and coatings.
ABSTRACT
The depth-profiles of accelerated aged triterpenoid dammar and mastic varnishes, which had been uncovered by optimized KrF excimer laser ablation (248 nm, 25 ns), were examined by ultraviolet-visible (UV/VIS) spectrophotometry and attenuated total reflection (ATR) Fourier transform infrared (FT-IR) spectroscopy. The results reflect both the optical properties at the bulk (UV/VIS) and the surface (ATR/FT-IR) and establish the presence of degradation gradients across the depth of the degraded natural resin films. It is demonstrated that the UV part of the ambient radiation is absorbed by the deteriorated surface and that the optical densities of the aged varnish decrease as a function of depth. The absorbed UV wavelengths at the surface and the depth-wise reduction of light intensity result in a depth-dependent decrease in carbonyl absorbance and an increase in C-H bending vibration modes of methylene species pointing to structural modification in the triterpenoid mixture across depth.
