Available online at http://www.journalijdr.

com

ISSN: 2230-9926 International Journal of Development Research

Vol. 07, Issue, 12, pp.17835-17845, December, 2017

ORIGINAL RESEARCH ARTICLEORIGINAL RESEARCH ARTICLE OPEN ACCESS

DIFFERENTIATION BLACK PIGMENTS IN “MAJA AND CELESTINA”, A PAINTING ON

ALABASTER BY FRANCISCO DE GOYA

*1Luis Rodrigo Rodríguez-Simón, 2Miguel Ángel León- Coloma

and 3Vicente del Sol-López

1PhD. Department of Paint and Restoration, Faculty of Fine Arts, University of Granada,
Av. Andalucía nº 38, 18071 Granada, Spain
2PhD. Department of Historical Heritage, Faculty of Humanities, University of Jaén,
Campus Las Lagunillas s/n, 23071 Jaén, Spain
3Proffesor, Department of Languages and Computer Systems, University of Granada,
Periodista Daniel Saucedo Aranda s/n E-18071, Granada, Spain

ARTICLE INFO ABSTRACT

Article History: Identifying and characterising the pigments forming part of a work of art is particularly relevant
Received 26th September, 2017 for the chronological authentication of a painting, as well as knowledge of the great masters
Received in revised form artistic resources, which could result in the work being catalogued. The aim of this research is to
22nd October, 2017 morphologically characterise and differentiate two black pigments of an organic nature, which are
Accepted 08th November, 2017 intrinsically mixed together and compacted by a binder. These pigments are part of a black
Published online 30th December, 2017 monochrome painting on alabaster by Francisco de Goya. The observation with SEM and EDX
microanalysis have allowed to identify and morphologically differentiate these two pigments:
Key Words: vegetable black or vine black and carbon black (lamp black). Thus, in the case of vine black
Francisco de Goya, 18th century, pigment, polygonal forms were observed that may indicate the rigid walls characteristic of
Painting, alabaster support, vegetable cells. Lamp black pigment can be associated withsmall spherical structures, apparently
Vine black pigment, lamp black pigment, homogeneous, which appear along with the polygonal vine black forms. We have suggested that
Scanning Electron Microscopes (SEM-EDX),
Goya mixed these two pigments to obtain a more stable pictorial mixture provided by the black
micro Raman spectroscopy (mRS),
Visible and near-infrared spectrophotometry.
vine pigment and a darker color by the lamp black pigment. The two black pigments that were
identified are bound together by a mixture of linseed oil and egg, denoting a tempera grassa
painting technique.
Highlights
 This study is based on a painting done on a translucent alabaster plate.
 Alabaster is a little used material as support in paintings, although it has been very used in
sculptures, altarpieces and covers.
 This painting reproduced an original pictorial composition by Goya, using only the colour
black.
 This innovative study proposes the morphological differentiation of vine black and lamp
black pigments.
 Both pigments are mixed and bound together forming a single colour.
 The morphological differentiation of vine black and lamp black pigments has been
undertaken based on original paint samples from an 18th century painting by Francisco de
Goya
 Via SEM-EDX it has been possible to morphologically differentiate vine black and lamp
black pigments based on the cellular structure of the former and the amorphous structure
of the latter.

Copyright ©2017, Luis Rodrigo Rodríguez-Simón et al. This is an open access article distributed under the Creative Commons Attribution License, which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Citation: Luis Rodrigo Rodríguez-Simón, Miguel Ángel León- Coloma and Vicente del Sol-López, 2017. “Differentiation black pigments in “maja and
celestina”, a painting on alabaster by francisco de goya”, International Journal of Development Research, 7, (12), 17835-17845.
17836 Luis Rodrigo Rodríguez-Simón et al. Differentiation black pigments in “maja and celestina”, a painting on alabaster by francisco de goya

INTRODUCTION (UV). The most used analytical and spectroscopic procedures

are: Optical Microscopy with transmitted and reflected
Identifying the components present in works of art constitutes illumination (OM), Scanning Electron Microscopes (SEM-
a research activity that has been being developed for several EDX) and Transmission Electron Microscopes (TEM), X Ray
decades (Gettens et al., 1966; Plester, 1966) because of interest Diffraction (XRD), Raman spectroscopy (RS) and micro
in finding out about the artistic materials and painting Raman spectroscopy (mRS), Visible and near-infrared
techniques used by artists in the creation of their works. spectrophotometry, Gas Chromatography-Mass Spectrometry
(GC-MS). By means of this equipment it has been possible to
Historiographical and technical precedents identify artistic materials, of an organic and non-organic
nature, present in works of art. This is achieved by interpreting
These raw materials and painting methods have been passed the corresponding spectrum and chromatograms obtained from
down throughout history in ancient manuscripts and treatises, each one of these instrumental techniques. In the case of
which have been compiled in specialist literature (Merrifield, SEM-EDX and XRF micro-analysis it is possible to identify
1967). Even the methods and material used by the grand the pigments and materials used as a base via their constituent
masters have reached us today (Eastlake 2011). In addition, chemical elements, captured in the corresponding spectrum
writings about different pigments and painting practice have (Spring, 2004, 2007; Favaro et al. 2012). Raman Spectroscopy
been preserved (Cennini, 1968; Leonardo da Vinci, 1995; also obtains spectrums with bands and peaks characteristic of
Vasari, 1960; Armenini, 2000; De Holanda, 2003;Pacheco, each pigment, based on its direct application onto the surface
1990; Palomino, 1988) and even formulas and formularies of the work and also on each layer of the corresponding
with prescriptions detailing the ingredients and the preparation transverse sections (Civici et al. 2005; Nevín,2008; Muralha et
of compounds (Gheroldi, 1995). Furthermore, there is a large al., 2012; Gutiérrez-Neira et al., 2013; Pozzi et al., 2014;
amount of literature that gathers detailed descriptions of Frano et al., 2014).
techniques, painting materials and their use in Art (Doerner,
1989; Mayer, 1985; Bazzi, 1965; Laurie, 1967; Thompson, Identification of black pigments of an organic nature.
1956). Other authors dedicate their work to the specific study Objectives, limitations and scope
of pigments and binders (Gettens and Stout, 1966; Montagna,
1993; Harley, 2001; Berrie, 2001). All these precedents have In the case of black pigments with an inorganic composition,
encouraged an interest in knowing works of arts internally, such as black lead oxides and manganese oxides, their
applying examination methods and analytical techniques for identification can be carried out by means of the above
the purpose of obtaining the maximum possible information analytical and spectroscopic techniques. These pigments are
about the usual materials and methods of the different painting recognised via the corresponding spectrum and their
schools introduced by the great masters, thus acquiring a deep constituent chemical elements, as well as their characteristic
understanding of their style and technique, of their hallmarks bands and peaks (Lahlil et al., 2012;Rampazzi et al., 2007).
and peculiarities. All these technical details will serve to Literature also exists on identifying the black pigments present
authenticate previously anonymous works of art, or reject in cave paintings (Chalmin et al., 2006; Vázquez et al., 2008;
those works of doubtful authorship. It is therefore vitally Jezequel et al., 2011; Eastaugh et al., 2004). In relation to
important to recognise pigments and clarify the creative black pigments of an organic nature, it is possible to identify
process based on a stratigraphic interpretation of samples and a them through SEM-EDX as they all have Carbon as a main
detailed observation of the painting's surface (density or element. Through this micro analytical technique, as has been
fluidity of the pictorial paste, graphics, texture and thickness of shown, these pigments are recognised based on the chemical
brushstrokes, superposition of layers, location and distribution elements they are composed of, including Carbon, (Rodríguez
of pigments etc.) (Rodríguez Simón, 2011, 2015). Simón et al., 2011; Tomasini et al., 2012a, 2012b, 2015).
However, when the black pigments form part of a painting it is
Current approaches to knowledge of materials and artistic difficult to characterise them, at both a structural and a
methods molecular level, based on stratigraphy. In this sense some
experiments have been carried out using Raman Spectroscopy
There is now regular research being carried out based on to identify black pigments based on carbon, taking actual
examination methods and analytical and spectroscopic pigments as a reference (Tomasini et al., 2012a, 2012b;
techniques for studying and researching works of art. The aim Coccato et al., 2015). The representative peaks have then been
is to identify the artistic materials present in the great compared to artistic samples in order to identify the black
paintings, as is the case of pigments and binders, and pigments present, taking into account the similarity between
determine the peculiarities each artist may have in the manner their characteristic Raman bands (Tomasini et al., 2015).
of using pigments. One example would be the mixture of
vermilion and red lead with cochineal lacquer used to achieve The objective of this study is to carry out a methodological test
the red of a Madonna's tunic (Rodríguez Simón, 2015). This on the differentiation of black pigments of an organic nature
approach is comparable to the study of the use of black forming part of a work of art, either in isolation or mixed with
pigments in the painting we are dealing with. The mixture of other pigments. We proposed evaluating their possible
different types to achieve a single colour black could constitute discrimination taking into account the morphological aspects
a peculiarity of the Aragonese painter. The scientific related to their internal structure, above all when pigments are
techniques that are systemically applied to the study and combined, forming a single colour for the entire pictorial
research of Artworks can be classified as examination composition, as occurs in this work by Goya. We there for
methods, based on electromagnetic radiation and on analytical proposed a multi-analytical approximation through the
and spectroscopic techniques. The examination methods are: X following techniques: SEM-EDX, mRS, Visible and near-
Rays (XR), Infrared Reflectography (IR), Scanning infrared spectrometry, Optical microscopy and Gas
Multispectral IR Reflectography and Ultraviolet Fluorescence chromatography/mass spectrometry. This article presents a
17837 International Journal of Development Research, Vol. 07, Issue, 12, pp.17835-17845, December, 2017

discussion about the limits and scope of the different methods

in characterising black pigments of an organic nature.
Recognising these black pigments is complicated in works of
art where dark colours predominate and even in other works
that are done solely with this colour, achieved with a single
black pigment or with a mixture of two or more. Our case
study is a monochrome painting in which only the colour black
predominates. It is achieved with the mixture of lamp black
and vine black; pigments that we have been able to identify
with SEM-EDX. However, it has not been possible to
differentiate between them or identify their location and
distribution in the pictorial strata as they form a uniform and
continuous layer, compacted by the binder. We therefore
proposed differentiation these black pigments through
complementary non-destructive analytical techniques, given
the small size of the work, such as Raman Spectroscopy
(Rodríguez Simón et al.,2012) and Visible Spectrometry-near
Infrared (Rodríguez Simón et al., 2013). These techniques did
not produce any results that we could consider conclusive.
They have been unable to help us differentiate between and
individually characterise the different types of black present in
the painting being studied, which were previously recognised
with SEM-EDX.

With the aim of furthering our research and taking as a

reference Cennino Cennini's descriptions of different ways of
making black (Cennini, 1968, 5, chapters XXXVI and Figure 1. Maja y Celestina by Francisco de Goya. Photograph of
XXXVII) and also the experiments of Winter (Winter et al., the painting (18.8 cm x 15.5 cm)
2007; Tomasini et al., 2012a, 2012b, 2015) and those of
Gettens and Stout (Gettens et al., 1966), we propose A small amount of powder from the painting, by a brushstroke
undertaking an analysis of the micro samples extracted from running along the edge of the alabaster.
the work studied, utilising the dramatic enlargement provided
by the Scanning Electron Microscope, as described in the Analytical Techniques
section on Materials and Methods. This technique has enabled
us to observe characterise and differentiate between these two These materials have been observed and analysed via the
black pigments based on their molecular structure, together following techniques:
with their micro analytical identification. Taking into account
the writings of Cennino Cennini (Cennini, 1968 –5),and the Scanning electron microscopy (SEM Leo 1430 VP) with
works of Montagna and (Montagna, 1993; Eastaugh, 2004), microanalysis of elements (EDX)applied to the stratigraphy
this study indistinctly records the black pigments studied as, on and also to a small portion of black-paint powder, from
the one hand, vegetable black or vine black obtained by brushstroke the edge of the work.
burning vine shootsor wood; and on the other hand, carbon
black or lamp black made by roasting mineral oil and also by Scanning electron microscopy, SEM Leo 1430VP, linked to a
burning linseed oil, coal, pitch, resins or waxes. system for the microanalysis of elements via energy-dispersive
X-ray spectroscopy, Inca 350, version 17 (hereinafter, SEM-
MATERIALS AND METHODS EDX). Scanning electron microscopy enables the identification
of elements with low atomic numbers, including carbon.
Brief description of the painting: Maja and celestina by Obtaining images of back-scattered electrons (BSE) shows the
Francisco de Goya (Rodríguez Simón, 2013) (Figure 1), in average atomic number of the pigments, and the images of
particular collection, is a painting done on a translucent secondary electrons (SE) provide information on texture and
alabaster plate with dimensions of 18.8 x 155cm and a structure, whilst analysis of the elements making up the
thickness of 16 mm. It is a monochrome painting in which pigments is undertaken via energy-dispersive X-ray
only varying intensities of the colour black are perceived in the spectroscopy (EDX). The SE and BSE images and analysis via
form of different fluid or opaque brushstrokes applied to the energy-dispersive X-ray spectroscopy were acquired at an
surface, depending on the luminosity and chiaroscuro of the acceleration voltage of 20 Kv. The spectra were acquired over
composition. Goya also plays with burin incisions in order to 50 seconds, with a resolution of 20 ev/Ch and an acquisition
delimit the forms and accentuate areas of greater luminosity. rate of 3000cps.

Materials Samples Confocal micro-Raman spectroscopy [mRS], applied “in

situ”, focusing the laser directly on to the surface of the work
The materials employed within this study are as follows: and also on the stratigraphy prepared via a microsample of the
painting. Raman spectra were obtained employing a an InVia
A stratigraphy of the painting, prepared from a microsample
Raman microscope (Renishaw) with a Raman signal
encased in methacrylate resin.
acquisition geometry of 180º (backscattering), a 50x lens
(numerical aperture of 0.75) and attenuating filters between
17838 Luis Rodrigo Rodríguez-Simón et al. Differentiation black pigments in “maja and celestina”, a painting on alabaster by francisco de goya

0.1% and 0.05% of maximum laser strength, the output power Visible and near-infrared spectrometry, applied “in situ” on to
being 20 mW. The equipment was fitted with a Leica DM LM the surface of the picture.
microscope, connected to a video camera, with a holographic
notch filter to eliminate Rayleigh dispersion, a 1200 L/mm The spectrophotometric data was collected using an Ocean
diffraction grating and a 400 x 575 pixels CCD-type detector. Optics USB2000+ spectrometer with a Labsphere integrating
Excited lines of both 514.5 and 785 nm in a diode laser were sphere, 8º/h geometry (specular component included) with
employed to analyse these types of pigment. Raman analysis 5/16 inch sample port diameter. A voltage stabilized 7Watt
was carried out on the stratigraphy and also directly on the tungsten-halogen lamp (mod. HL-2000-FHSA) optimized from
work. The confocal properties of the equipment enable us to 360-2000 nm range was used together with Spectralon diffuse
place the painting directly under the objective lens of the white (99% reflectance) as reflectance standard.
microscope connected to the spectrometer, allowing us to carry Other instrumental techniques
out non-destructive in situ analysis.
Optical microscopy is used in order to observe the stratigraphy
or transverse section of the painting. Preliminary examination
of the painting samples was carried out, on the one hand, via a
polarised light optical microscope, with parallel and crossed
nicols (Carl Zeiss, Jenapol U model). On the other hand, an
ultraviolet microscope was employed (Olympus, CX41RF
model) affording information on the fluorescence given off by
the pigments and binding agents. The information provided by
the optical microscope is essential for recognising the internal
micro structure resulting from the creative process followed by
the painter, which is vitally important for authenticating the
work. It also allows the microscopic image to be visualised
with the sequence of strata and the actual colours of the
constituent pigments of each one of the layers, their
distribution, milling and texture. With ultraviolet illumination
it is possible to better distinguish the stratigraphic structuring
due to the fluorescence emitted by both pigments and binders.

Figure 3a. Spectrum obtained via SEM-EDX microanalysis, with

the characteristic peaks of gypsum that makes up the alabaster
medium.

Figure 3b. Spectrum obtained via SEM-EDX microanalysis, with

the characteristic peaks of calcium carbonate and the mix of
calcium and magnesium carbonate, secondary components of the
gypsum, in its alabaster form, and also silicates originating from
clays, which are normally natural contaminants of gypsum
Figure 2a. Photograph obtained by Optical microscopy
Figures 2b, 2c. Photograph obtained via scanning electron Gas chromatography/mass spectrometry. It is undertaken
microscopy of the stratigraphy extracted from the painting, based on micro samples extracted from the pictorial surface.
shown Pictorial layer and under strong magnification, wherein it
is possible to distinguish the gypseous structure of the alabaster This technology enables identification of the binding agents
that serves as a medium (figure 2c) that provide cohesion to the pigments, allowing us to
determine the painting technique.
17839 International Journal of Development Research, Vol. 07, Issue, 12, pp.17835-17845, December, 2017

The samples were treated with Meth-Prep II to detect oils, In some areas, depending on the fluidity and intensity of the
resins and waxes. In the case of carbohydrates and proteins, brushstrokes, there is only a thin stratum, but in others there
hydrolysis and subsequent derivatisation via silylation with are two overlapping layers which are denser and more opaque.
TBDMSTFA in pyridine was employed. The latter is the case of the intense black of the room’s rear
wall, against which the figures of Maja and Celestina are
silhouetted, applied by the painter to give depth to the scene.
RESULTS AND DISCUSSION
Analysis of the stratigraphy via SEM-EDX
Analysis with optical microscope
EDX microanalysis enabled us to identify calcium sulphate as
Analysis of this monochrome painting by Goya was carried the main component (Figure 3a), calcium carbonate and a mix
out, firstly, via a single stratigraphy (Figures 2a, 2b, 2c) that, of calcium and magnesium carbonate as secondary
under the optical microscope, provided us with information on components of the gypsum, given its alabaster form, and also
the internal structure and the sequence of layers of which it is silicates originating from clays, which are natural
composed: an initial layer, corresponding to the alabaster contaminants of gypsum (Figure 3b). These components
medium, and two further superficial layers that make up the confirm the gypseous nature of the material employed as a
black paint layer. medium. The painting layers of this cross-section also revealed
the presence of carbon black (lamp black), vine black or
vegetable black, gold, quartz and earth as pigments employed
by Goya to create the work. Identification (Rodríguez Simón et
al., 2011) was carried out on the basis of the chemical
elements present in spectra captured with SEM-EDX spectra
(Figures 4a, 4b, 4c).

Figure 4a. Spectrum corresponding to the vine black pigment,

with the characteristic peaks of carbon, and potassium and
calcium as a trace element.

Figure 5a. Spectrum showing the characteristic peaks of lead

white and bone black pigments that were found to be present in
the painting at a trace level

Figure 4b. Spectrum corresponding to the carbon black pigment,

with its characteristic peak

Figure 5b. Spectrum corresponding to the black pigment made

up of iron oxides, detected by a high iron peak

SEM-EDX observation under high magnification

However, in this study our aim is to make advances in the
differentiation of these two black colours, which are mixed
together within the painting, proving difficult to distinguish via
SEM-EDX, as carbon is the main component in each case.
Therefore, to identify them via microanalysis when employing
Figure 4c. Spectrum corresponding to the small flakes of gold leaf this instrumental technique, we must make recourse to the
included within the mix of the two black pigments, with its identification and detection of trace elements within the
characteristic peaks, which illustrate the purity of the gold. existing pigments, such as potassium, and calcium, which is
17840 Luis Rodrigo Rodríguez-Simón et al. Differentiation black pigments in “maja and celestina”, a painting on alabaster by francisco de goya

characteristic of vine black or vegetable black (Charcoal), We have suggested that the painter mixed the two black
minor elements present in plant cells. (Montagna, 1993; pigments in order to obtain a more stable colour. Therefore,
Tomasini, 2012) (Figure4a). Our aim is to study these black the two samples were studied in detail under high
pigments taking as a reference their morphological magnifications, whilst simultaneously undertaking the
differentiation based on the experiments of Winter and microanalysis associated with this technique, with the aim of
Tomasini, (Winter et al., 2007; Tomasini, 2012a, 2012b, 2015) verifying the characterisation of the internal particles. In each
- 42,43, 45, 49), using as a tool the dramatic enlargements case, the characteristic elements of the pigments were
made possible by the Electron Microscope to visualise the identified, revealing themselves to be lamp black, vine black
materials selected in our research, which are detailed in the or vegetable black (Charcoal) and gold. Oxygen peaks have
section on Materials and Methods: stratigraphy and black also been detected in the corresponding spectra. The presence
powder from a brushstroke on the edge of the alabaster. The of oxygen was indicative of oxidized compounds arising from
stratigraphy and the small particles of black powder were duly incomplete combustionof wood by fire (Tomasini et al., 2012).
prepared for observation with an electron microscope. It is Moreover, both the stratigraphy and powder extracted from the
these that have enabled the two black pigments; vine black and painting contained fragments of other black pigments, such as
lamp black to be characterised and differentiated. bone black, lead white and iron oxides (Figures5a, 5b).

Figure 6a-6b-6c. Detail 1: Polygonal forms that, in our view, indicate the rigid walls characteristic of vegetable cells from vine black
pigment. This Polygonal configurations covered by spherical structures, made up of very small particles, enveloping the entire
ensemble and which may be ascribed to the amorphous structure of carbon black pigment (lamp black)

Figure 7. Observation of the mix of vine black and lamp black pigments under high magnification. Polygonal shapes characteristic of
the walls of plant cells are observed and also and also tiny spherical structures linked by the binders are observed
17841 International Journal of Development Research, Vol. 07, Issue, 12, pp.17835-17845, December, 2017

Figure 8 - a,b,c.- Polygonal forms that, in our view, indicate the rigid walls characteristic of vegetable cells from vine black pigment.
This Polygonal configurations covered by undefined formations made up of very small particles, which are deposited on the
configurations, enveloping the entire ensemble and which may be ascribed to the amorphous structure of carbon black pigment (lamp
black)

Figure 9.Observation of the mix of vine black and carbon black pigments under high magnification.
The silhouette of the rigid wall characteristic of plant cells has been observed.

We suggest that the presence of traces of lead white and bone carbon black provides a strong colour, but it has It has a weak
black pigments could be considered as additives, adulterations consistency derived from its origin, acquiring a greater degree
or contaminations of the brush or the palette. We have also of solidity when mixed with vine black, which is more
thought that these iron oxides detected with SEM-EDX are of consistent due to the rigid structure of the cell walls of the
black color, since, in the observation of the cross-section with wood, a pigment that does not offer the same capacity to
optical microscopy, no iron oxide particles of red color nor of blacken. This reflection could be related to Tomasini's
iron oxides of yellow color have been detected. However, comment to about the presence of iron detected in the
based on this premise, we suggest that mix of lamp black and referenced samples of vine black: the presence of iron may be
vine black with a view to obtaining a more stable colour: related to the addition of iron oxides to obtain a dark-colored
17842 Luis Rodrigo Rodríguez-Simón et al. Differentiation black pigments in “maja and celestina”, a painting on alabaster by francisco de goya

Figure 10. Photograph of the painting “Maja y Celestina”, indicating the points on the surface of the painting at which Raman
microspectrometry analysis was carried out, showing the corresponding spectra with arrows, wherein the three spectra at the top
correspond to carbon and the three at the bottom, to the gypsum of the alabaster.

Figure 11. Measurements of spectral reflectance in different

areas of work, taken in situ on the surface of the painting
17843 International Journal of Development Research, Vol. 07, Issue, 12, pp.17835-17845, December, 2017

material (Tomasini et al., 2012). This approach could justify (alabaster), along with bands of 494 and 1136 cm-1 (Figure 10).
the presence of iron peaks in the spectra captured by SEM- As Tomasini points out, these results are characteristic bands
EDX in the paint object of our study. When observing the of carbon. Nevertheless, it is very difficult to discriminate the
stratigraphy under high magnification, the two pigments in sourceof carbon-based pigments because their Raman spectra
question could not be distinguished at a morphological level, are very similar, although differences in band positions,
given the cohesion between the pictorial strata brought about intensities, and bandwidths may be observed after a detailed
by the binding agent, compacting the mixture in such a manner study of the spectra. The stratigraphy was also analysed via
that we were unable to visualise the existence of structures at application of the Raman laser at 514.5 nm and 785 nm., again
an internal level. Nevertheless, as indicated above, analysis of capturing the spectra corresponding to carbon and alabaster.
the samples via SEM-EDX enabled us to identify the
characteristic chemical elements associated with each pigment, Analysis via visible and near-infrared spectrometry
as shown in the corresponding spectra. However, the sample As with Raman Spectroscopy, the analyses with Visible-near
entailing powder from brushstroke from the painting enabled Infrared Spectrometry were carried out in situ, applying the
us to characterise the two pigments on the basis of their colorimeter directly onto the surface of the work, choosing
morphology, as high magnification has uncovered structures those points that presented a different degree of intensity in the
that has made differentiation viable. Thus, in the case of the brushstroke colour, ranging from a translucent tonality to an
vine black pigment or vegetable black, polygonal forms were intense black. The aim was to confirm the similarity or
observed that may indicate the rigid walls characteristic of difference between the spectral bands captured in each one,
vegetable cells, given its botanical origin. (Figure 6a, 6b, 6c). and be able to determine the characterisation of lamp black and
SEM-EDX confirmed the presence of Carbon as a major vine black pigments, using non-destructive methods. This is
element and potassium and calcium, a trace element that similar to the experiments on a Roman fresco wall paint dated
characterises vegetable or vine black (Montagna, 1993) around 30 BC (Gatta et al., 2012) carried out by Gatha and
(Figure 4a), are expected to derive from plant material collaborators (2012). These authors suggest that
(Tomasini et al., 2012). This Polygonal configurations are thermogravimetry and differential thermo analysis techniques
mixed by spherical structures, apparently homogeneous, made (TG-DTG) are useful for authenticating black powder
up of very small particles, which are deposited on the pigments, but also that an old black pigment could only be
polygonal forms, enveloping the entire ensemble and which identified in situ with Colorimetry. In our case, Spectral
may be ascribed to structure of carbon black pigment (lamp reflectance measurements obtained in different samples of the
black) (Figure 7). These corpuscles may be due to the work show spectral curves between 360 nm and 1020 nm
spherical structurewith smooth surfaces of the lamp black without characteristic traces. The peak observed at 922 nm is a
pigment (Tomasini, 2012; Winter et al., 2007) Figure 8a, 8b, peak within the transmission of the fibre optic employed. Both
8c, and Figure 9). SEM-EDX indicated a high carbon peak in the form of spectral distribution and the a* b* coordinates of
the corresponding spectrumby their high content of carbon the different samples present similar values, and seem to
(Rodríguez Simón et al., 2011; Tomasini et al., 2012) (Figure correspond to a mixture of several black pigments rather than
4b).Furthermore, in the two samples (stratigraphy and matching one specific pigment (Gatta et al., 2012) (Figure 11).
powdered paint), observation under high magnification
enabled us to morphologically verify the presence of minute Identification of binders
gold leaf flakes (Rodríguez Simón et al., 2011) that are
included within the two pigments in question: golden particles The identification of binders has been done by Rodríguez
that have been identified via SEM-EDX as gold of a very high Simón and Parra Crego through Gas Chromatography-Mass
purity. Spectrometry. The following results were obtained:
Raman analysis
The peaks that appear in the chromatogram corresponding to
Analysis of the stratigraphy was also undertaken employing a the analysis of fatty acids correspond to azelaic, palmitic and
complementary technique for pigment identification: stearic acids, with a Palmitic/Stearic proportion of 1.67 and an
Azelaic/Palmitic of 0.2. These values indicate the
Raman spectroscopy, which failed to provide conclusive characterisation of a drying oil such as linseed. Other minor
results in terms of the differentiation of these colours. Raman components are also recognised such as traces of pine resin
spectroscopy analysis was undertaken “in situ”, focusing the and beeswax. In relation to the binders of a protein nature, the
laser directly on to the surface of the painting, selecting analysis of amino acids from the whole sample indicates the
different points on the basis of the degree of transparency and determination of animal glue due to the presence of
the intensity of the colour: hydroxyproline and a high percentage of glycine. In addition, a
second analysis of the insoluble residue detected a significant
 Focused on intense black. increase in amino acids such as glutamic acid and aspartic
 Focused on a more translucent hue. acid, indicating the existence of egg albumen (Rodríguez
 Focused on the ash coloured base coat applied before Simón et al., 2011). The presence of these peaks in the
the painting was commenced. corresponding chromatograms suggests that the binder would
 Focused on a clear area where the white of the alabaster be made from a mixture of linseed oil and egg. The animal
comes to the fore. glue comes from impregnating the alabaster in order to limit its
In the three spectra captured from different intensities of the porosity and prepare it for receiving the layers of paint.
black colour, the bands that characterise carbon can be Conclusion
observed (1340w and 1595vs cm-1) (Pagés-Camagnaet al.,
2007); and in the fourth spectrum we observe an intense band The recognition, identification and characterisation of
of approximately 1000 cm-1 which characterises gypsum pigments present in an artistic sample, as well as their
17844 Luis Rodrigo Rodríguez-Simón et al. Differentiation black pigments in “maja and celestina”, a painting on alabaster by francisco de goya

arrangement, location, distribution and proportion in the Chalmin, E., Vignaud, C., Salomon, H., Farges, F., Susini, J.,
sequence of layers forming part of the internal structure of a Menu, M. 2006. Mineral discovered in Paleolithic black
painting, is crucially important for assigning a chronology to pigments by transmission electron microscopy and micro-
the work in question and for cataloguing it within a specific X-ray absorption near-edge structure. Applied Physics A
painting school. We've experimentedalso that the combination 83: 213-218.
of the different analytical techniques used has not facilitated De Holanda, F. 2003. De la pintura antigua y El diálogo de la
the definitive characterisation of the black pigments of an Pintura. Madrid: VisorLibros.
organic nature, as they are bound together forming a consistent Doerner, M. 1989. Los materiales de pintura y su empleo en el
pictorial mass. Because of this difficulty, we suggest Arte. 5ª ed. Barcelona: Reverté.
evaluating their possible discrimination on the basis of the Eastaugh N, Walsh V, Chaplin T, Siddall R. 2004. Pigment
morphological differences found in the dramatically enlarged Compendium: A Dictionary and Optical Microscopy of
images captured by the scanning electron microscope, bearing Historic Pigments. Oxford: Elsevier Butterworth-
in mind the cellular aspects related to their internal structure. Heinemann.
This is particularly important in this case as the pigments are Eastlake, C.L. 2001. Methods and materials of painting of the
combined, forming a single colour black. This is the reason for Great Schools and Masters. New York: Dover
starting from a minute quantity of small particles of black PublicationsInc.
powder from a brushstroke on the edge of the alabaster, which Favaro, M., Guastoni, A., Marini, F., Bianchin, S., Gambirasi,
has given us the possibility of characterising and A. 2012. Characterization of lapis lazuli and corresponding
differentiating the black pigment of an organic nature present purified pigments for a provenance study of ultramarine
in this painting by Francisco de Goya. Thus, with the dramatic pigments used in Works of art. Anal Bioanal Chemistry,
enlargements achieved with the scanning electron microscope, vol. 402: 2195-2208- DOI: 10.1007/s00216-011-5645-4.
in the case of the vine black pigment we have observed some Frano, K.a., Mayhew, H. E., Svoboda, S. A., Wustholz, K.L.
polygonal forms that could indicate the rigid wall 2014. Combined SERS and Raman analysis for the
characteristic of vegetable cells. The lamp black pigment can identification of red pigments in cross-sections from
be connected to the smallest particles with spherical historic oil paintings. Analyst, 139: 6450-6455.
structures. These appear bound to the polygonal forms of vine Gatta, T., Campanella, L., Coluzza, C., Mambro, V.,
black, or vegetable black as a result of these two pigments Postorino, P., Tomassetti, M., Visco, G. 2012.
having been intrinsically mixed with the binder. This latter Characterization of black pigment used in 30 BC fresco
aspect shows the need for the samples to be magnified with an Wall paint using instrumental methods and chemometry.
electron microscope, due to the minute size of the powder Chemistry Central Journal 6 (Suppl 2): 52.
particles obtained from the brushstroke on the edge of the Gettens, R. J., and E. W. FitzHugh. 1066. Azurite and blue
alabaster. Gold leaf particles, within the mix of blacks, were verditer. Studies in Conservation, 11: 54-61.
also observed, indicating the painter's aesthetic intention to Gettens, R.J. and Stout, G. 1966. Painting Materials. New
give luminosity and brilliance to the intense black York: Dover Publications Inc.
predominating in certain areas of the work. The chemical Gheroldi, V. 1995. Ricette e Ricettari. Tre fonti per la storia
information obtained on the materials and technology used in delle tecniche delle arti alla Biblioteca Queriniana di
the manufacture of the paintings contributed to increase our Brescia (sec. XVI-XVII). Brescia: Comune di Brescia.
knowledge on about the paintings by Francisco de Goya. Gutiérrez-Neira, P.C., Agulló-Rueda, F., Climent-Font, A.,
Garrido, C. 2013. Raman spectroscopy analysis of
Acknowledgements
pigments on Diego Velázquez paintings. Vibrational
Andalusian Research Groups HUM-839. Analyses were Spectroscopy, 69: 13-20.
performed in the Scientific Instrumentation Centre (CIC) of Harley, R.D. 2001. Artists’ Pigments c. 1600-1835. London:
the University of Granada (Spain). Archetype Publicationes.
Hofmann, M. 2008. Il Mellon Digital Documentation Project. I
REFERENCES dieci quadri di Rafaello della National Gallery di Londra.
Armenini, G.B. 2000. De los verdaderos preceptos de la Kermes, 2008, 72: 25-27.
pintura. Madrid: Visor Libros. Jezequel, P., Wille, G., Bény, C., Delotme, F., Dean-Prost, V.,
Bazzi, M. 1965. Enciclopedia de las Técnicas Pictóricas. Cottier, R., Breton, J., Duré, F., Despriee, J. 2011.
Barcelona-Madrid: Noguer. Characterization and origin of black and red Magdalenian
Berrie, B. H. 2001. Artists’ Pigments. A Handbook of Their pigments from Grottes de la Garenne (Callée moyenne de
History and Charasteristics. Vol.4. London: Archetype la Creuse-France): a mineralogical and geochemical
Publications. approach of the study of pehistorical paintings. Journal or
Cennini C. 1968. The Craftsman’s Handbook “Il Libro Archaeological Science, Elsevier, 38 (6): 1165-1172.
dell’Arte”. New York: Dover Publications Inc. Lahlil, S., Lebon, M., Beck, L., Rousselière, H., Vignaud, C.,
Ciatti, M. and Brunetti, B.G. 2012. Caravaggio’s Painting Reiche, I., Menu, M., Paillet, P., Plassard, F. 2012. The
Technique. In Proceedings of the CHARISMA workshop. first in situ micro-Raman spectroscopic analysis of
Firenze: Nardini Editore, Kermesquaderni. prehistoric cave art of Rouffignac St-Cernin, France.
Civici, N., Demko, O., Clark, R.J.H. 2005. Identification of Journal Raman Spectroscopy, 43:1637-1643.
pigments used on late 17th century Albanian icons by total Laurie, A.P. 1967. The Painter’s Methods and Materials. New
reflection X-ray fluorescence and Raman microscopy. York: Dover Publications Inc.
Journal of Cultural Heritage, 2005, 6: 157-164. Leonardo da Vinci. 1995. Tratado de la Pintura. Madrid:
Coccato, A., Jehlicka, J., Moens, L., Vandenabeele, P. 2015. Ediciones Akal.
Raman spectroscopy for the investigation of carbon-based Mayer, R. 1985. Materiales y técnicas del Arte. Madrid:
black pigments. Journal Raman Spectroscopy, 46: 1003- Hermann Blume.
1015.
17845 International Journal of Development Research, Vol. 07, Issue, 12, pp.17835-17845, December, 2017

Merrifield, M. 1967. Medieval and Renaissance Treatises on Rodríguez-Simón, L.R., Parra Crego, E. 2011. Caracterización
the Arts of Painting. New York: Dover Publications Inc. de pigmentos y aglutinantes mediante VPSEM y GC-MS
Montagna, G. 1993. I pigmenti. Prontuario per l’arte e il en una pintura firmada por Francisco de Goya: Maja y
restauro. Firenze: Nardini. Celestina. En: Heritage and Design of Geometrical Forms.
Muralha, V.S.F., Burgio, L., and Clark, R.J.H. 2012. Raman Granada: Universidad de Granada: 385-408.
spectroscopy analysis of pigments on 16-17th c. Persian Roy, A. Spring, M. 2007. Raphael’s Painting Technique: In
manuscripts. Spectrochimica Acta Part A, 92: 21-28. Working practices before Rome. Proceedings of the Eu-
Nevin, A. Loring Melia, J., Osticioli, I., Gautier, G., ARTECH workshop. Firenze: Nardini Editore,
Colombini, M.P. 2008. The identificacion of copper Kermesquaderni.
oxalates in a 16th century Cypriot exterior wall painting Spring, M. 2004).Perugino’s Painting Materials: Analysis and
using micro FTIR, micro Raman spectroscopy and Gas context within sixteenth-century easel painting. In Brunetti,
Chromatography-Mass Spectrometry. Journal of Cultural B.G, Seccaroni, C., Sgamellotti, A. (eds). The Painting
Heritage, 9:154-161. Technique of Pietro Vannucci, called Il Perugino.
Pacheco, F. 1990. El Arte de la Pintura. Madrid: Cátedra. Proceediings of the Labs TECH Workshop. Firenze:
Pagés-Camagna, S.,Duval, A., Guicharnaud, H. 2004. Study of Nardini Editore, Kermesquaderni, pp. 21-28.
Gustave Moreau’s black drawings: identification of the Spring, M. 2007. Raphael’s Materials: Some new discoveries
graphic materials by Raman microspectrometry and PIXE, and their context within early sixteenth-century painting. In
J. Raman Spectroscopy, 35, 628-632. Roy, A. and Spring, M. (eds). Proceedings of the Eu-
Palomino, A. 1988. El museo pictórico y escala óptica. ARTECH workshop. Firenze: Nardini Editore,
Práctica de la pintura. Madrid: Aguilar Maior. Kermesquaderni, pp. 77-86.
Plester, J. 1966. Ultramarine, natural and artificial. Studies in Thompson, D. V. 1956. The materials and techniques of
Conservation, 11: 62-91. medieval painting. New York: Dover Publications Inc.
Pozzi, F., Jan van den Berg, K., Fiedler, I., and Casadio, F. Tomasini, E., Siracusano, G., Maier, M.S. 2012a.
2014. A systematic analysis of red lake pigments in French Spectroscopic, morphological and chemical
Impressionist and Post-Impressionist paintings by surface- characterization of historic pigments based on carbon.
enhanced Raman spectroscopy (SERS). Journal of Raman Paths for the identification of an artistic pigment.
Spectroscopy, vol. 45 Issue 11-12: 119-1126. Microchemical Journal, 102: 28-37.
Rampazzi, L., Campo, L., Cariati, F., Tanda, G., Colombini, Tomasini, E.P., Gómez, B., Halac, E.B., Reinoso, M., Di
M.P. 2007. Prehistoric wall paintings: The case of the Liscia, E.J., Siracusano, G., Maier, M.S. 2015.
Domus de Janas Necropolis (Sardinia, Italy). Identificatiion of carbón-based black pigments in four
Archaeometry, 49: 559-569. South American polychrome wooden sculpturesby Raman
Rodríguez-Simón, L.R. 2011. Maja y Celestina. Una pintura microscopy. Heritage Science, 3:19. DOI 10.1186/s40494-
sobre alabastro firmada por Francisco de Goya. El proceso 015-0049-y.
creativo y la técnica de ejecución pictórica. Kermes, 84: Tomasini, E.P., Halac, E.B., Reinoso, M., Di Liscia, E.J.,
37-44. Maier, M.S. 2012. Micro-Raman spectroscopy of carbón-
Rodríguez-Simón, L.R. 2013. Maja y Celestina. Una nueva based black pigments. Journal of Raman Spectroscopy, 43:
pintura sobre alabastro en el catálogo de Francisco de 1671-1675.
Goya. Cuadernos de Arte de la Universidad de Granada, Vasari, G. 1960. On Technique. New York: Dover
44: 145-170. Publications Inc.
Rodríguez-Simón, L.R. 2015. El proceso creativo y la Vázquez, C., Maier, M.S., Parera, S.D., Yacobaccio, H., Solá,
estructuración estratigráfica como señas de identidad y P. 2008. Combining TXRF, FT-IR and GC-MS
autenticidad. La pequeña Madonna di Foligno de Rafael, information for identification of inorganic and organic
como caso de estudio. PH INVESTIGACIÓN, 5: 45-67. components in black pigments of rock art from Alero
Rodríguez-Simón, L.R., Del Sol López, V., Manzano Moreno, Hornillos 2 (Jujuy, Argentina). Anal Bioanal Chem,
E., Navas Iglesias, N., López-Ramírez, M. R. 2013. 391:1381-1387.
Advances in the study of black pigments via spectroscopic Winter, J., West FitzHugh, E. 2007. Pigments Based on
techniques in a painting by Francisco de Goya. In: Carbon. In Berrie, B.H. (ed.). Artists’Pigments: A
TECHNART 2013. Analytical Spectroscopy in Art and Handbook of Their History and Characteristics, Vol.4.
Archaeology, Abstract book, Amsterdam: Rijksmuseum, p. London: Archetype Publications, pp. 1-37.
86.
Rodríguez-Simón, L.R., López-Ramírez, M.R., Navas, N.,
Manzano, E. 2012. Black pigments identification on
alabaster painting: Maja y Celestina by Francisco de Goya,
in situ mRS and SEM-EDX analysis. In: IRUG 10 book of
abstracts.Barcelona: Universidad de Barcelona, p. 192-
193.

*******