CONTRIBUTED ARTICLE

15. Ways of Seeing:

Fourier Transform Raman Spectroscopy
in the examination of artist’s materials.
Alex Drake and Kristine Moore*
‡
Department of Pharmacy,
King’s College London,
Manresa Road,
London SW3 6LX

*To whom correspondence should be addressed:

e-mail:kristine.moore@kcl.ac.uk

Abstract

A brief survey of the challenges presented by,

and some of the techniques that have been used
in, the examination of artist’s materials is
presented. Pigmented egg yolk tempera and oil
films were examined by both visible & near
infrared Raman spectroscopy. The potential of
Fourier Transform Raman Spectroscopy (FTR) as
a non-destructive technique for the examination
of artist’s materials is discussed.

Keywords:

FTR, EGG YOLK TEMPERA, OIL PAINT, PIGMENTS,

Introduction

Paints made using the egg yolk of the domestic fowl (Gallus gallus) have been
documented since at least AD 1140 [1] and are well known for their durability [2]
and relative resistance to treatments. The so called "drying oil" paints gradually
superseded tempera in Europe during the fifteenth century. However, as it became
known, pictures in oil were less resistant to change than those of egg tempera but
the oils had offered advantages in composition. Despite the hardy nature of
tempera pictures, some undesirable changes may occur.

A requirement exists to distinguish between works executed in egg yolk tempera,

oil, egg and oil, and more complex intermediate mixtures for some, or all, of the
following reasons: to assist in the completion of the documentation of a picture, to
allow informed selection of the appropriate preventative conservation measures
that will allow the art work to be seen by future generations as the artist intended,
and to contribute to the discussion on the question of attribution. An
understanding of the mechanisms underlying the progressive ageing of films will
assist in the identification of egg yolk and egg yolk mixtures in paint media.

Identification of media by Fourier Transform Infrared Spectroscopy (FTIR) alone

can be unreliable as absorbance from the pigment can obscure bands due the
media. In addition, infrared spectra of aged films are inevitably much more
complex than those of the initial constituents. Conservators are understandably
cautious in releasing anything but the smallest, inconspicuous, samples from
works of art and so a further constraint is placed on the technique used for
identification. A combination of methods, for example, FTIR/Differential
Scanning Calorimetry, may be used to give a greater degree of certainty in
identification. The sequential application of techniques to a sample usually
follows a non-destructive to "more-destructive" technique rationale. Identification
of proteins or peptides by staining, or by a separative technique, is undesirable as
the former method is unreliable and both methods are inevitably destructive.
Many techniques have been applied to pictures to find a combination of non-
destructive techniques or, preferably, a non invasive technique that allows
conclusive identification of both the media and pigment present.

Fluorescence has limited the application of Raman spectroscopy, using

conventional lasers, in this field but the technique has proved useful in the
identification of extremely small pigment particles on, or very near, the surface of
manuscripts and ceramics [3, 4] A recent survey [5] showed 56 out of a total of 64
pigments in use before ~AD 1850 to produced high quality spectra by Raman
microscopy. Ostensibly, the application of FTR to the study of both media and
pigments is very inviting. The technique using near infrared excitation is, on the
whole, free of the fluorescence problems associated with the blue-green lasers. It
is, usually, non-destructive and a real possibility exists for in situ, non destructive
study of the materials with which pictures are made. The use of FTR in tandem
with FTIR will yield the "whole vibrational picture" [6].

FTR using a remote probe sampling system has recently been used to determine
the source of an ivory inlay [7]. The introduction of a non-invasive, non
destructive, technique, such as FTR, yielding molecular information in situ on the
chemical species, both organic and inorganic, within a picture could be a major
advance in this field. To speculate wildly - if FTR, or perhaps Raman Optical
Activity Spectroscopy, could provide the ability to ascertain the absolute age of a
representative sample of media within a picture there would be major implications
for the art world

Professor Hendra at Southampton University kindly helped me to make

exploratory investigations into the application of FTR to the identification of
media.

A consideration of some of the limitations

in the application of FTIR to the study of
ageing of paint films.

In practice, when an infrared spectroscopist is asked by a conservationist to

address a particular query, the question is very rarely "what is it?" but rather "is it
oil or is it egg? glue or gum? is this resin the same as the other resin?" Contextual
information concerning location of the picture, likely provenance, condition,
pigments present (by elemental analysis, scanning electron microscopy) and
information from optical and polarised light microscopy provide data to assist in
the interpretation of the spectrum.

Fundamental research starts with known materials and simple situations and
common practice is to study the processes of ageing that may occur in simple
media mixtures with single effects, for example, light or thermal ageing, and
predict and match the behaviour of authentic films when possible. FTIR is a
mature technique, readily available in these situations, at relatively low cost, for
the examination of even extremely small quantities of paint samples.

The mechanisms underlying the ageing of oil are still the subject of debate [8] and
Raman spectroscopy has contributed to a revival of this discussion. The proposed
mechanisms underlying the drying of oil have been used as a point of departure
for the discussion of those underlying the drying and ageing of tempera as the
triacylglycerol (TAG) fractions are common. Tempera films differ from those of
oil in possessing three different, significant, components: protein, water and
phospholipid. We are aware that tempera and oil films have different physical
properties, there must be a physico-chemical basis for this.

Egg tempera and oil, when unpigmented, are easily distinguished by FTIR - the
simultaneous presence of four characteristic bands Amide A, B, I & II and the
common ester carbonyl at ~1740 cm-1 identifying the protein/oil mixture.
However the addition of pigment often masks a significant and diagnostic portion
of the spectrum and leads, in turn, to difficulty in interpreting age and pigment
dependent changes. Unpigmented media have been studied to provide a baseline
in uncovering age dependent changes in media mixtures but they are rarely, if
ever, used in pictures.

Workers in this field have used sodium chloride or potassium bromide (KBr)
plates as supports for fresh films and KBr disks as method for investigating
historic, and therefore scarce and valuable, samples [9]. Hygroscopic materials of
this type may be suitable for oil media where, we presume, there is little or no
water involvement with the stabilisation of the film. However, we have shown
that it is possible to remove water from some tempera paints and there is probably
a reversible exchange of water with the ambient air. We have also demonstrated
that it appears possible to reproduce some of the effects of ageing by the
desiccation of tempera samples and this may confirm the role of water in the
inhibition of lipid oxidation. The application of a technique that does not have the
effect of abstracting water from films is desirable.

The use of FTIR micro-sampling (beam condenser with diamond cell) provides a
method whereby water is allowed to remain in contact with the sample. However,
there are concerns that intensity information obtained when using this technique
can be misleading as the light throughput is compromised both by beam
condensing and the crystal lattice absorption of the diamond cell Sections of
appropriate thickness can be prepared for FTIR transmission microscopy.
However, specimens are often "gritty" proving difficult to microtome and
embedding resins can infiltrate the sample to a varying extent. Although spectral
subtraction of the embedding media can be applied, media peaks can be swamped
by those of the resin. Workers at the National Gallery in London have
successfully used silver chloride (AgCl) as an embedding material for thin
sections from pictures [10]. The AgCl is transparent in the mid IR and so spectra
of the media/pigment only may be obtained but, difficulties exist in supporting
sections of this type and they lack long term stability as the AgCl eventually
discolours. The preparation of cryosections is theoretically interesting but the
same difficulties of supporting the section exist.

The difficulty of sampling a homogenous section of a sample within even an

extremely small section of pigmented media must not be ignored. We are
inevitably sampling a molecular array containing areas of media:media,
media:pigment and media air:interaction We see part of, but, a mixed picture.
Raman spectroscopy will encounter the inadequate spatial resolution problem and
so the sampling of an inhomogenous molecular array, is common to both
techniques. FTR offers the advantages of new and complementary information
without a requirement for excessive manipulation, adulteration or destruction of
sample.

FTR Spectroscopy at Southampton

Experimental

Semi quantitative media rich films were prepared by the traditional tempera
method. Organic eggs (Best Before 24/12/97, used on 11/12/97) were obtained
from Waitrose Supermarket, King’s Road, London.
Pigments were obtained from L. Cornelissen & Son Ltd, Great Russel St, London.
London tap water supplied by Thames Water, calcium concentration ~ 4mmol/l.
The oil paints were obtained from Daler Rowney (Bracknell, Berks) - Titanium
white (009) and alizarin crimson (515).
The pigment was initially triturated, mixed with water and further grinding took
place to thoroughly wet the pigment. The wetted pigment is then briefly mixed
with yolk before application, in this case, onto glass microscope slides. The films
were been allowed to dry for ~ 7 days in ambient conditions.

The commercial oil paints were prepared by painting directly painting onto
microscope slides and allowed to dry for ~ 12 days.

Instrumental

Perkin Elmer System 2000. Excitation wavelength 1064nm, Backscattering

configuration, 8 cm-1 resolution.

Results and Discussion

FTR spectrum of egg yolk tempera

Although lacking suitable backing material, to enhance the collection of the

scattered light, a spectrum was obtained and tentative and alternative assignments
have been made.

Figure 1. FTR spectrum - Egg yolk tempera

Raman Intensity Attributed to Comments

Shift

3012 medium C cis unsaturation TAG

2900+/- strong  -CH protein & TAG

100

2721 weak  CH(O) aldehyde ?

 1741 weak  C=O ester carbonyl TAG

1658 medium  C=C unsaturated TAG or protein amide

/Amide I groups

1522 weak ? unassigned

1441 strong  CH CH2 deformation - protein & TAG /

NH2 (7)

1303 weak  CH CH2 twist rock - protein & TAG

1270 medium Amide III /   CN +  NH / cis unsaturation / CH2

C=H (7)

1160 weak  C-O ? alcohol TAG

1082 medium  C-O O-CH2- TAG

Table 1. Tentative assignments of bands present in egg yolk tempera

(TAG = Triacylglycerol)

FTR spectra of pigmented media

All the samples examined gave Raman spectra, except for vermilion (HgS)
tempera. Sample decomposition appeared to be occurring when attempts were
made to collect the spectrum.