Towards Building A Cathodoluminescence (CL) Database For Pigments .

Palamara et al. Herit Sci(2021) 9:100lead-based white pigment and can even be extended todescribe lead chloride oxides, lead phosphates and leadsulfates; it usually refers to lead carbonate hydroxide, 2PbCO3.Pb(OH)2 [31].Lead carbonate hydroxide is chemically equivalentto the naturally occurring hydrocerrusite, which isextremely rare and therefore rarely used as a pigmentsource. During the Roman period, Vitruvius in the 1stc. BC and Pliny in the 1st c. AD describe the synthesisof this mineral, called “cerussa” at the time, by steepinglead in vinegar [26]. The processes used by the Romansare the basis of the medieval to 17th c. technologies forlead white manufacture. A thorough description of themost common production methods of lead white untilthe early 20th c. is given by Eastaugh et al. [26].The pigment is permanent, relatively stable in all media(but particularly when used in oil). On the contrary, itwas rarely used in fresco, where lime white was substituted. It was commonly adulterated with other white pigments, particularly chalk, baryte and kaolinite. The use oflead white has been widely reviewed [indicative publications: 32, 33].The concern over lead poisoning increased during theIndustrial Revolution. Although lead white continued tobe marketed, alone and combined with other pigments,its presence sharply decreased in the first half of the 20thc., from nearly 100% to less than 10% by 1945 and it waswidely abandoned in the period after World War II [34].Zinc oxideIn the second half of the 18th c. an effort began to findviable substitutes for lead white, in response to theincreasing awareness of the health hazards entailed inits manufacture and use [32]. The search was oriented inparticular towards investigating zinc oxide (ZnO) for thispurpose. Although known since antiquity as a by-product of brass production and for its medicinal properties,this substance was seemingly never used as a pigment[33, 35]. The development and refinement of methodsfor producing a non-poisonous white pigment from zincmetals or ore, and the improvement of the material itself,lead to the production of a pigment, which was first commercialised by Winsor & Newton in 1834 under the nameChinese White and marketed as an artists’ pigment in awatercolour medium. Shortly thereafter it was improvedfor use in oil, when Leclaire succeeded in improving itsdrying and covering properties, inferior until then to thealso still less costly lead white. By 1859, zinc oxide white,which had a further advantage over lead-based pigmentsbecause it did not blacken in the presence of hydrogensulfide, was being produced on an industrial scale inEurope and the United States.Page 3 of 14Barium‑based pigmentsBesides zinc oxide white and kaolin, which was still beingused primarily for grounds and as an additive and filler,several barium-based materials (such as barium sulfate, BaSO4) were also proposed as artists’ pigments, eitherin the form of natural ground barytes, or the more puresynthetically produced pigments such as blanc fixe [36].The reduced hiding power of these substances, however, tended to restrict their use in the paint industry asextenders for lead, zinc, and later, titanium compounds,or as a base for lakes. These pigments were introducedcommercially in the early 19th c.; after 1950, althoughthey were still available both in their natural and synthetic forms, they sharply declined in production forartistic purposes.Another white material developed in this period wasthe composite pigment lithopone ( BaSO4.ZnS), whichwas obtained by precipitating zinc sulfide with bariumsulfate. It was first produced according to patents grantedin France around 1850 [35]. Initially, the most commonlithopone pigments were produced using equivalentsolutions of barium sulfide and zinc sulfate, which endedup producing a mixture of approximately 29.5 percentzinc sulfide and 70.5 percent barium sulfate. However,purer and higher strength varieties have since been manufactured, with varying ratios of the two ingredients; twogrades of lithopone, known as gold and bronze seal, contain between 40 and 50 percent zinc sulfide, resulting ina pigment with much more hiding power and tinctorialstrength [37].Despite the cheapness of its manufacturing processesand good properties as pigment, lithopone had the tendency to darken when exposed to sunlight. In the late1920s, a small amount of cobalt, varying from 0.02 to0.5% of the zinc content, was added prior to the calcination process to prevent discoloration. Nevertheless, theusage of lithopone as an artists’ pigment was difficult toestablish and it was primarily used as a cheap extenderfor other white pigments, like ZnO [38].Titanium whiteThe elementary metal titanium, never found unboundfrom other elements in nature, was first discovered inEngland in 1791 by William Gregor in the iron titaniumoxide ilmenite, and by M.H. Klaproth also in rutile oresin Germany in 1795, who confirmed it is a new elementand gave it its name. Before that, the use of titaniferousminerals for the production of pigments is not attested,though in Mayapan site (Yucatan Peninsula, Mexico) asmall amount of nanocrystalline TiO2 particles (in rutileform) has been consistently detected using phase mapping in red pigment samples [39]. During the 19th c.

Palamara et al. Herit Sci(2021) 9:100several attempts were carried out to produce colouredpigments from natural ground titaniferous minerals,including titanium dioxide, with limited success. Mostof these attempts focused on the most common crystallographic form of TiO2, rutile; of the other two forms,anatase and brookite, the former was used rarely and thelatter does not seem to have ever been used directly as apigment [40].The first successful attempts to manufacture superiorquality synthetic products took place practically simultaneously in Europe and the US in the early 20th c. Thefirst commercially successful composite pigments ofanatase were obtained in the 1920s, through precipitation of anatase titanium dioxide onto a barium sulfatebase. Despite the fact that the rutile form was muchless rare and was known to possess better hiding powerand weathering properties than anatase, difficulties inits refinement continued to privilege the latter. Only in1937 were successful methods for producing syntheticrutile developed, with the pigment becoming widelyavailable in the market in the second half of the 20th c.[26].The initially high cost of titanium dioxide whitesshortly diminished, as various drawbacks typical of theearly manufacturing methods were overcome. Combinedwith the high quality of the produced pigment, titaniumwhite almost completely supplanted the other white pigments by the middle of the 20th c. [40].Binding mediaA binding medium is the film-forming component ofpaint. A pigment should not dissolve in the bindingmedium nor be affected by it. However, it is well established that different binding media can strongly affectthe paint, especially after ageing. Additionally, bindingmedia, which are usually organic substances, can significantly hinder the identification of pigments, by altering their signals as determined by various analyticaltechniques.Before the Middle Ages, artists used pigments in beeswax (encaustic) melted and manipulated with hot rods.Since the early Middle Ages, paintings on wood panelshave traditionally been produced in egg tempera. Eggyolk is a semi-opaque medium: it can be used translucentor nearly opaque.During the Renaissance, egg tempera was graduallysupplanted in popularity by oil paint on canvas. In oilpainting, the most popular oil for binding pigment, thinning paint and varnishing finished paintings is linseed oil.The linseed oil comes from the flax seed, a common fibercrop. Linseed oil tends to dry yellow and can change thehue of the colour [41].Page 4 of 14Safflower, walnut and poppy seed oils are sometimesused in formulating lighter colors like white becausethey “yellow” less on drying than linseed oil. They havethe drawback of drying more slowly and may not providethe strongest paint film [41]. Poppy seed oil, for example,takes 5–7 days to dry, compared to 3–5 days for linseedoil.MethodsResearch aimThe main aim of the present work is the formation of arobust database of characteristic CL spectra of pigments,focusing primarily on those which were most commonlyused from antiquity until today. This will allow for a moreextensive application of SEM/CL in the examination ofpaintings and painted materials. White pigments havebeen selected as the first case study, due to their significance and frequency of use, since white pigments werealso applied on the ground layers or mixed with otherpigments in most of the painting layers.Seven of the most common white pigments (calcite,kaolinite, lead white, zinc oxide, barium sulfate, lithoponeand titanium white) were analysed in pure form, usingSEM/CL. In order to facilitate comparison with otherdatabases, EDS and RAMAN analyses were also carriedout. Additionally, parameters such as the ageing of pigments and the effect of binding media were also studied,by the analysis of especially prepared samples. Finally, thespectra of pigments in pure powder form were comparedto similar pigments identified on the surface of two paintings (from the 19th and 20th c., respectively).SamplesIt is common for manufacturers of contemporary paintsand dry materials to omit mentioning some of the components, such as technological additives for impartingcertain properties to paints or inert fillers to reduce thecost of dry pigments and paints [24]. Since the purposeof this study is to create a database of the CL signal ofpigments, samples in pure form were selected for analysis. More specifically, lead carbonate (PbCO3), zinc oxide(ZnO) and barium sulfate (BaSO4) commercial samples(Sigma Aldrich) were analysed in powder form. Lithopone was also a commercial sample (“Artists pigmentsPremium Kunstler-pigments”, lithopone no. 108), madein Germany by H. Schmincke & Co. The calcite ( CaCO3)was a pure spar sample; both the calcite and the kaolinitesamples came from the Geology scientific collection ofthe National Museum of Natural Sciences-CSIC, Madrid,Spain.The titanium dioxide pigment corresponds to therutile crystallographic form; the sample has undergonenatural ageing of more than 15 years. Additionally, 4

Palamara et al. Herit Sci(2021) 9:100reference samples, produced in 2001, consist of a mixtureof Ti white with 4 of the most common types of bindingmedia, namely: egg yolk, walnut oil, linseed oil and poppyseed oil. For the preparation of the egg tempera samples,the egg yolk was separated from the egg white, and thenremoved from its skin. For one part of egg yolk, one partof vinegar and two parts of water were added. The mixture was stirred very well and mixed with the medium.All samples were left at room temperature for two daysto dry before undergoing the accelerating ageing processproposed by Meilunas et al. [42] (oxidative type of ageing): samples were heated in air at 120 C for 24 h andthen cooled again to 25 C. For the heating process a Gallenhamp—Hotbox Oven of size 2, with stainless steel lining and fan for even heat distribution was used.Finally, three microsamples of two paintings, representing cross-sections with multiple colour layers each, werealso analysed. Two samples come from a 19th c. painting entitled “Game” (oil on canvas, with inv. No P838) byan unknown artist and one sample comes from a 20th c.painting entitled “Hydra” (oil on cloth, with inv. no K595)by Economou Michael [43]. They both belong to the collection of the National Gallery – Alexandros SoutzosMuseum in Greece. The microsamples were detached bythe conservators of the National Gallery before the conservation process of the paintings and were embedded inresin and polished.MethodsThe micromorphology, topography and distribution ofthe components in the samples were determined using aFEI INSPECT Scanning Electron Microscope (ESEM) ofthe Museo Nacional Ciencias Naturales (Madrid, Spain).The ESEM microscope in low vacuum mode can workwith hydrated samples to be studied in their original stateusing the large field detector (LFD), since it is close to thesample in order to avoid electron losses, and the BackScattering Electron Detector (BSED).The SEM resolution at low-vacuum was at 4.0 nm at30 kV (BSED). Energy Dispersive Spectrometry (EDS)of the samples was carried out with an energy dispersiveX-ray spectrometer by Oxford Instruments, using INCAsoftware for the quantification of the data. In EDS analysis an accelerating voltage of 20 kV was used. Precalibration tests of SEM/EDS chemical measurements werepreviously performed on internal standards to improvethe ZAF correction procedure (Z: atomic number; A:Absorption effect; F: Fluorescence effect).The SEM setting previously described has MONOCL3Gatan (CL) detectors, making it possible to work in panchromatic and monochromatic mode with a PA-3 photomultiplier attached to the ESEM. The photomultipliertube covers a spectral range of 250–850 nm and is morePage 5 of 14sensitive in the blue parts of the spectrum. A retractable parabolic diamond mirror and a photomultipliertube were used to collect and amplify the CL signal.No filters were applied to standardize the sensitivity ofthe photomultiplier tube. The samples were positionedat 16.23 mm beneath the bottom of the CL mirror. Theexcitation for CL measurements was provided at 30 kVelectron beam. The settings of the analyses were as follows: dwell time: 1.5 s, range: 600 nm, step size: 1.5 nm.Depending on the sample (homogeneity of material,preparation method) CL analyses were carried out eitheron bulk surfaces or individual inclusions. All CL spectrapresented below were the outcomes of single analyses butare considered representative of multiple analyses carriedout on different areas of each sample.The samples were analysed by Raman microscopy ofthe Museo Nacional Ciencias Naturales –CSIC (Madrid,Spain). The micro-Raman spectroscopy analysis wasperformed by both single spectra using Thermo-FischerDXR Raman Microscope (West Palm Beach, FL 33407,USA) which has a point-and shoot Raman capability ofone micron spatial resolution with an Olympus BXRLA2 Microscope and CCD (1024 256 pixels) detector,motorized xy stage, auto-focus and microscope objectives Olympus UIS2 series (West Palm Beach, FL 33407,USA) all controlled through OMNIC 8.3 software. Thelight at 780 nm of a frequency doubled Nd:YVO4 DPSSsolid laser (maximum power 14mW) was used for excitation. The sample was inspected with the 20 objectiveto select areas. The spectra were obtained with using the20 and 50 objectives of the confocal 25 µm slit andgrating of 900 lines/mm. These conditions and excitations at 780 nm give an average spectral resolution of2- 4 cm 1 in the wavenumber range of 200–3200 cm 1.The sample spot size was approximately 1–2 µm, inaccordance with the objective used. An integration timeof 10 s 4 accumulations was enough to get acceptable results. The calibration and align spectrograph werechecked using pure polythene.ResultsCharacteristic CL spectraOf the above mentioned 7 common white pigments, kaolinite, calcite and zinc oxide have been studied in the pastusing SEM/CL [44–48]. The detailed analysis of these 7samples suggests that they all present CL spectra withcharacteristic bands, as shown in the following figures.Based on the CL panchromatic images, an evaluation canbe made on the strength of the signal, as brighter areassuggest a stronger CL signal. Based on this observation,information can be drawn on the homogeneity of thematerial. More importantly, a pigment showing strongsignal will be easier identified in a real case study, i.e.

Palamara et al. Herit Sci(2021) 9:100when present in small quantities, mixed with other elements and aged. In order to facilitate comparison withother pigment databases, EDS and Raman spectra of eachpigment analysed are also presented in the Supplementary Material.The calcium carbonate sample analysed (in pure calciteform, as shown by its Raman spectrum shown in Additional file 1: Table S1) presents a clear CL spectrum, witha strong band at 416 nm, a band at 460 nm and a wideband at 765 nm. Two shoulders are also noted at 334 and386 nm (Fig. 1). The common defects of geological calcitic material have been discussed in detail in literature[46, 47].Kaolinite also presents a clear CL spectrum, with astrong wide band at approximately 365 nm; and twosmaller bands at 678 and 754 nm. Two shoulders are alsonoted at 334 and 386 nm (Fig. 2). A detailed descriptionof the main defect centers of kaolinite is given by Götzeet al. [44]. The sample analysed consisted of grains withdiverse chemical and CL signal, as expected; the mainbands of the spectrum, however, are consistently present,allowing for the identification of the pigment.As mentioned before, the lead carbonate selected foranalysis was in the form of P bCO3. The pigment produced low CL signal, suggesting that its identification willbe difficult if present in small quantities. The spectrum,however, shows a characteristic band at 474 and a smallerband at 436 nm (Fig. 3).The titanium dioxide sample analysed (in the form ofrutile, as shown by its Raman spectrum shown in Additional file 1: Table S1) produced low CL signal, as can alsobe seen from the low intensity of the panchromatic image(inset image of Fig. 4). Therefore, the identification of thepigment, if present in small quantities, will be more difficult than the other white pigments examined. This hasalso been noted by Kadikova et al. [24]. However, thespectrum shows two characteristic sharp bands at 434and 472 nm, as well as a wider band at 800 nm (Fig. 4).It should be highlighted that though the analysed sample had undergone natural ageing of minimum 15 years,the resulting spectra are identical to those presented byKadikova et al. [24], which corresponded to a titaniumwhite pigment of the “Schmincke” paint set.The zinc oxide sample produced a CL spectrum witha strong sharp band at 390 nm (Fig. 5); the wider bandat 776 nm is the second order of the diffraction grating,associated with the design of the instrument. A smallwide band at approximately 495 nm is also noted. Adetailed description of the emission centers and defectsof ZnO is given by Ton-That and Phillips [48]. It shouldbe highlighted that zinc oxide produced very strong signal, suggesting that it would be possible to identify evenvery small quantities of the pigment.Page 6 of 14The barium sulfate pigment analysed produced a CLspectrum with a characteristic wide band at approximately 556 nm (Fig. 6, top); a small wide band at 390 nmis also noted.1 The lithopone sample also produced acharacteristic spectrum with multiple bands: a strongband at 364, smaller bands at 468, 572, 702 and 764 nmand a shoulder at 428 nm (Fig. 6, bottom).The clear distinction of the CL spectrum of lithoponecompared to the spectra of barium sulfate and zinc oxideis very significant. The identification of lithopone is notstraightforward with elemental analysis techniques, suchas X-ray fluorescence or SEM/EDS, since the produceddata does not permit the distinction between lithoponefrom mixtures of barium sulfate and zinc sulfide orzinc oxide present as unprecipitated compounds [38].Even with spectroscopic techniques, such as Raman,it is very difficult to identify the pigments used, when acombination of any of these three pigments is used (e.g.in a mixture of lithopone with ZnO, the characteristicbands of ZnO coincide with the typical spectrum of purelithopone).Monochromatic imagesTaking monochromatic images for specific wavelengthsof emission, it is possible to identify the distribution ofa pigment, even if multiple pigments with a similar elemental composition are present on the same area. Forexample, on one area of the micro sample of the painting “Game”, a complicated elemen

e potential of applying SEM/CL for the identica-tion of pigments presents strong interest, since it could successfully tackle some of the analytical problems which can signicantly complicate the analysis of paintings and painted materials (e.g. pottery). e characterization of pigments presents multiple diculties, the most impor-