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In this study, the structural characteristics and thermal degradation behaviour of barium, calcium and zinc soaps of hemp seed oil prepared using the metathesis method are reported. Scanning electron micrographs of the metal soaps showed similar plate-like microstructures and are indicative of an orderly packed particulate structure. The bands at 1509, 1539 and 1543 cm-1 in the FTIR spectra showed the association of the carboxylate ion with Ba, Ca and Zn ions respectively The thermal decomposition consisted of one single step on the weight loss - temperature curves located around 250 - 450 ℃ for all the divalent metal soaps at the various heating rates and the observed loss in weight which occurred before 200 ℃ was minimal (< 10%). The average values of the apparent activation energy for the thermal process were 18.73, 13.77 and 8.48 kJ/mol for Zn-HSO, Ca-HSO and Ba-HSO respectively. [ABSTRACT FROM AUTHOR]

Up to 70 % of the oil paintings conserved in collections present metal soaps, which result from the chemical reaction between metal ions present in the painted layers and free fatty acids from the lipidic binders. In recent decades, conservators and conservation scientists have been systematically identifying various and frequent conservation problems that can be linked to the formation of metal soaps. It is also increasingly recognized that metal soap formation may not compromise the integrity of paint so there is a need for careful assessment of the implications of metal soaps for conservation. This review aims to critically assess scientific literature related to commonly adopted analytical techniques for the analysis of metal soaps in oil paintings. A comparison of different analytical methods is provided, highlighting advantages associated with each, as well as limitations identified through the analysis of reference materials and applications to the analysis of samples from historical paintings. [ABSTRACT FROM AUTHOR]

Metal soaps are formed in paint layers thorough the reaction of metal ions of pigments and fatty acids of organic binders. In this study, micro-ATR-FTIR spectroscopic imaging was used to analyse the formation of lead soaps in oil-based paint layers in relation to their exposure to moisture sources. The investigations were carried out on authentic samples of complex stratigraphies from cold painted terracotta statues (Sacred Mount, Varallo, UNESCO) and different IR-active lead white pigments, organic materials, and lead soaps were discriminated. The saponification of selected paint layers was correlated to the conservation history, the manufacturing technique, and the build-up of layers. The presence of hydrophilic layers within the stratigraphy and their role as a further water source are discussed. Furthermore, the modifications experienced by lead-based pigments from the core of an intact grain of pigment towards the newly formed decay phases were investigated via a novel approach based on shift of the peak for the corresponding spectral bands and their integrated absorbance in the ATR-FTIR spectra. Qualitative information on the spatial distribution from the chemical images was combined with quantitative information on the peak shift to evaluate the different manufacture (lead carbonate, basic lead carbonate) or the extent of decay undergone by the lead-based pigments as a function of their grain size, contiguous layers, and moisture source. Similar results, having a high impact on heritage science and analytical chemistry, allow developing up-to-date conservation strategies by connecting an advanced knowledge of the materials to the social and conservation history of artefacts. [ABSTRACT FROM AUTHOR]

Metal soaps or metal alkanoates are metal–organic complexes held together with metal cations and the functional groups of hydrocarbon chains. They can be synthesized at a high yield by simply mixing the metal and organic sources, forming crystalline frameworks with diverse topology, and have been studied in the past because of their rich polymorphism‐like liquid crystals. Their ability to melt while retaining the crystalline properties upon cooling is unique among nanoporous materials and is especially attractive for membrane fabrication. Herein, metal soaps as a new class of material for molecular separation are reported. Three metal soaps, Ca(SO4C12H25)2, Zn(COOC6H13)2, and Cu(COOC9H19)2, hosting lamellar structure with molecular‐sized channels are synthesized. They are processed in thin, intergrown, polycrystalline films on porous substrates by two scalable methods, interfacial crystallization and melting with an extremely small processing time (a minute to an hour). The resulting crystalline films are oriented with the alkyl chains perpendicular to the porous substrate which favors molecular transport. The prepared membranes demonstrate attractive gas separation behavior, e.g., 300‐nm‐thick Ca(SO4C12H25)2 membrane prepared in a minute using interfacial crystallization yields H2 permeance of 6.1 × 10−7 mol m−2 s−1 Pa−1 with H2/CO2 selectivity of 10.5. [ABSTRACT FROM AUTHOR]

The lack of an appropriate methodology makes numerous important issues related to miniature paintings unresolved—despite the fact that the portrait miniatures of the seventeenth to the nineteenth century represent a highly specific and significant field of European fine art. One of these issues is represented by chemical degradation of miniatures and its analytical evidence. Fragility, variability of the employed materials, and detailed execution make their analysis highly challenging—since no sampling is usually allowed and any change on their surface is immediately noticeable. Therefore, this study focused on finding a fully non-invasive multi-analytical approach to describe degradation processes resulting from the interaction of lead pigments and oils. For this purpose, a representative set of miniature portraits on various supports (ivory, metal, glass) has been selected. For the first time, Pb carboxylates (lead soaps) have been evidenced in miniatures painted in oil and also in a combined technique (gum + oil). Their distribution and crystallinity was described by a combination of X-ray-based (X-ray fluorescence and X-ray diffraction) and micro-spectroscopic methods. At the same time, a number of new findings about the employed painting technique and involvement of various pigments in the degradation processes were obtained. For example, a possible saponification of a mixed Pb-Sn-Sb yellow was indicated for the first time. Although the degradation is clearly at an advanced stage, it has not shown yet any visible symptoms that might warn restorers and curators. Therefore, without targeted analysis, it would remain overlooked. [ABSTRACT FROM AUTHOR]

Soaps are a class of surface active compounds derived from natural oils and fats. Double decomposition reactions permit the synthesis of metallic soaps, which are long-chain carboxylates of metal ions, from alkaline ones such as sodium, potassium or ammonium soaps. Metallic soaps are commercially important as they find use in diverse applications such as driers in paints or inks, components of lubricating greases, heat stabilizers for plastics (especially PVC), catalysts and water proofing agents, fuel additives and cosmetic products amongst others. Many of these applications are related to the thermal properties of these compounds and the thermal behaviour of metal soaps in terms of decomposition processes is of great importance. Rubber seed oil (RSO) which is an unsaturated triglyceride abundantly available in Nigeria, India and Australia is an excellent starting material for metal soaps. In this study rubber seed oil having 2.2% myristic acid, 7.6% palmitic acid, 10.7% stearic acid, 20.61% oleic acid, 36.62% linoleic acid, 22.5% linolenic acid was used in making barium, calcium, cadmium and zinc soaps. The thermal behaviour of soaps (Ba, Ca, Cd and Zn) of rubber seed oil for use as additives in the processing of poly(vinyl chloride) (PVC) was investigated by thermal gravimetry and differential scanning calorimetry. The stability of the soaps was examined by thermogravimetry up to 873 K at a constant heating rate of 10 °C min. The soaps were found to be thermally stable up to 473 K as they recorded less than 5% mass loss at this temperature with values of apparent activation energy for decomposition varying from 52 to 96 kJ mol. Differential scanning calorimetric studies of the soaps revealed melting and decomposition behaviour of metal soaps. [ABSTRACT FROM AUTHOR]

During a routine condition survey in 2007 at the Georgia O'Keeffe Museum in Santa Fe, micro-protrusions were found scattered across the surfaces of the artist's oil paintings produced between 1920 and 1950. In many of her works, including Pedernal (1941) and A Man from the Desert (1941), lead soaps were found aggregated at the painting surface, forcing the surrounding paint to deform into pin-sized protrusions. The structure and composition of the protrusions was analyzed to determine why they formed. Microsamples were removed from four of O'Keeffe's paintings and investigated using a combination of SEM–EDX, GC–MS, and FT-IR. The combined GC–MS and FT-IR results indicate that the protrusions contain primarily lead carboxylates. The results obtained for a series of ground samples removed from four different paintings were then compared with samples collected from a commercially pre-primed canvas roll found in the artist's house in Ghost Ranch, NM. We identified two different types of canvases: i) a commercially pre-primed canvas and ii) artist primed canvas. This commercially pre-primed canvas roll has a similar morphology to the ground layers in her paintings that contain protrusions additionally these grounds were found to contain an excess of free fatty acids and metal carboxylates (lead soaps) based on a comparison to canvases the artist primed herself. Based on the analytical results from the four paintings and the commercial pre-primed canvas, we concluded that the artist's use of this particular commercially pre-primed canvas between 1920 and 1950 play an important role in the observed micro-protrusions. [ABSTRACT FROM AUTHOR]

Metal soaps pose significant concerns in the preservation of paintings made with oil as a binding medium. In highly alkaline environments, metal soap aggregates may undergo mineralization processes with the formation of new phases, such as carbonates, chlorides, oxides and sulfates of the metal cations that are present in pigments or paint additives. In this work, we report new examples of the mineralization of lead soaps in paint-cross sections taken from a late-medieval panel painting owned by the Museum of Cultural History at the University of Oslo. Scientific analyses were carried out with optical microscopy under UV and visible light, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and Raman spectroscopy to investigate and characterize the nature of the compounds present in the samples. Lead (II,IV) oxide, which is presumed to be a secondary product in the mineralization of lead soaps, has been identified in lead-based paint. Unlabelled Image • Mineralized lead soaps were identified and investigated in paint samples from a late medieval panel painting. • Identification of secondary products in lead soaps. • Discrimination of new products and degradation products in the paint film. [ABSTRACT FROM AUTHOR]

Metal soaps and resinates are known to be spontaneously formed in artistic paintings, as a product of the reaction between aliphatic and terpenoid acids released by hydrolysis and oxidation of the organic media and certain cations contained in some inorganic pigments. In this paper we present an optimization and the validation of a GC/MS method for the qualitative and quantitative analysis of mixtures of terpenoid acids and aliphatic mono and dicarboxylic acids and metal carboxylates of terpenoid and aliphatic mono and dicarboxylic acids in the same paint microsample. This is based on a two-step analytical approach entailing the subsequent use of two silylating agents, N,O-bis(trimethylsilyl)trifluoroacetamide for the analysis of free acids and metal carboxylates, and 1,1,1,3,3,3-hexamethyldisilazane for the analysis of free acids. The application of this approach is possible because of the good stability at room temperature of the TMS derivatives of aliphatic and terpenoid species, characterized by high boiling points and relatively low vapour pressures. The method was then applied to the characterization of samples collected from two reference paint layers aged for 20 years, a paint sample taken from a pulpit, and sample of the varnish coating of a wooden writing desk, both from the second half of the seventeenth century. [ABSTRACT FROM AUTHOR]