Insight into the chemistry of deteriorated smalt pigment through analysis of samples from paintings

in the National Gallery London

Extended Abstract
Marika Spring

When the blue cobalt glass pigment smalt degrades, it not only loses its colour, but causes
yellowing of the oil so that the paint becomes brownish-yellow or greenish-grey. Often, this is
accompanied by other paint defects such as drying cracks and patchy blanching. The paint can be
lighter at the surface, as if the binding medium has disintegrated and is scattering light, or as if some
kind of efflorescence has occurred. It is clear from the appearance of areas of degraded smalt on
paintings that changes are occurring to the binding medium as well as the pigment.

It has already been shown with elemental and molecular mapping techniques that when smalt-
containing oil paint deteriorates the alkaline component of the glass, which in the case of smalt is
potassium, is lost from the pigment particles and migrates into the binding medium, where it has the
potential to cause concurrent alteration and degradation of the oil [1–3]. Possible processes include
reaction with carboxylic acids in the oil to form potassium fatty acid soaps, or perhaps with anion
sources in the environment to form species such as carbonates and sulphates (analogous to those
that are found on the surface of degraded vessel glass). This paper summarises recent studies of
discoloured smalt in eight National Gallery paintings, which investigate this process further. Paint
samples were examined using light microscopy, energy dispersive X-ray analysis in the scanning
electron microscope (SEM–EDX) and Fourier transform infrared microscopy (FTIR). The work
was carried out together with Catherine Higgitt and David Saunders and has been published in
detail in Volume 26 (2005) of the National Gallery Technical Bulletin [4].

SEM–EDX analysis of sky paint from Paolo Fiammingo’s The Sons of Boreas pursuing the
Harpies (NG 5467) illustrated the relationship between loss of colour and leaching of potassium
from the smalt particles (Fig. 1). Where the smalt is mixed with lead white, in the upper layer of the
cross section, it is well preserved; quantitative analysis showed that it contains around 13–14%
weight potassium. The smalt in the lower layer, mixed with only a little lead white, is degraded; the
paint is yellowish in colour, the pigment has lost its colour almost entirely and analysis showed it to
contain only 1–2% potassium (Table 1). The same pattern was observed in all the paintings in the
study.

Fig.1. Sky paint from Paolo Fiammingo’s The

Sons of Boreas pursuing the Harpies (NG
5467). The smalt in the upper layer, mixed
with lead white, is well preserved. The lower
yellow layer also contains smalt, but mixed
with only a little lead white; the pigment has
faded leaving only the yellow colour of the oil
binding medium.

Table 1. Quantitative analysis by SEM–EDX of degraded and undegraded smalt in the sample in Fig.1
(weight % oxide)
SiO2 K2O FeO CoO NiO As2O3 Bi2O3
 Upper layer: well 62–8 13–14 3.6–5.1 6.5–7.5 0.9–1.3 5.4–8.6 1.1–1.7
preserved smalt
Underlayer: degraded 76–78 1.6–2.2 5.1–5.7 4.2–5.5 0.3–0.4 8.6–9.1 0.1–0.4
smalt

It is known from historical documentary sources that smalt was available to artists in various grades
with different colour intensities, but it can be difficult to distinguish between pigment that is
degraded and that which has always been rather grey in hue. Quantitative analysis of smalt pigment
by SEM–EDX has proved to be a useful method of distinguishing between deteriorated and well-
preserved pigment based on the potassium content. Additional information such as the presence and
quantity of impurities associated with the cobalt ore used to manufacture the blue glass pigment was
also gained. The results in Table 1 show that the smalt in the painting by Paolo Fiammingo
contains, in addition to cobalt, a significant amount of arsenic and small quantities of iron, nickel
and bismuth. These originate from the cobalt ore used to colour the glass, and reflect the
geographical location of the mineral deposit. All the examples in the study, which date from
between the sixteenth and eighteenth centuries, were found to contain the same impurities.

Elemental mapping by SEM–EDX of cross sections also gave interesting results. Christ’s cloak in
The Conversion of the Magdalen attributed to Pedro Campaña (NG 1241) is now yellow-brown in
colour because it was painted with smalt. The mapping results on a cross section of paint from the
cloak showed that not only had the potassium leached from the smalt pigment particles into the
binding medium around them, but it had migrated to the surface forming a crust. A little cobalt and
nickel were also found in the surface crust, but this was not seen in the other samples studied, which
suggests that it only occurs when degradation is severe. It is of course cobalt that gives the glass
pigment its blue colour, but in the other samples the colour was lost even if cobalt was still present,
indicating that the change in environment in the glass when potassium is lost is sufficient to change
the colour. This is in agreement with the literature on the deterioration of vessel glass, which states
that although the first step in the deterioration process is loss of alkali, transition metals such as
cobalt and nickel can be depleted in very degraded glass.

Extensive research has been done on the deterioration of window and vessel glass which is useful
when considering the degradation of smalt pigment in oil. The research reports that the leached
alkali goes on to react with anions in the environment to form a complex crust on the surface which
can contain various salts such as arcanite (K2SO4), syngenite (K2SO4·CaSO4·H2O), as well as
calcium carbonate, sulphate and oxalate. The source of calcium in these complex crusts is not the
glass itself, but airborne particles in dirt that are gradually deposited on the surface and become
incorporated into the crust through reaction with the rather alkaline and hygroscopic salts initially
formed. Biodeterioration is also thought to play a role, manifested by the presence of calcium
oxalate. The salts formed depend on the environment. For example deteriorated glass which has
been kept in wooden showcases that are giving off formic acid has been found to contain sodium
and potassium formate in the crust. It seems possible, therefore, that in degraded smalt oil paint
potassium soaps could form by reaction with fatty acids in the oil.

The samples were examined using FTIR microscopy to attempt to determine whether there was any
evidence that salts or soaps had formed. The results were very consistent, and those from Joachim
Beuckelaer’s The Four Elements: Fire (NG 6588) were typical (Figure 2).
Fig. 2 Joachim Beuckelaer, The Four Elements: Fire (NG 6588). Infrared spectrum of the discoloured
smalt layer in the serving girl’s beige apron.

The major peak in the spectrum is the broad band at just above 1000 cm-1, which is from the smalt
pigment. A band is also present at 1562 cm-1, which can be assigned to the asymmetric stretch of
potassium soaps, demonstrating that the leached potassium has reacted with carboxylic acids in the
oil. It is not possible, however, to determine whether any other salts that have been found on vessel
glass, such as potassium sulphates and carbonates, have been formed because the characteristic
bands would be obscured by those from the smalt pigment. However, the peak at around 1649 cm-1,
as well as a smaller very sharp peak at 1324 cm-1, indicate that the sample contains calcium oxalate,
which has also been found as a degradation product in the crusts on the surface of vessel glass. In
the sample from the painting attributed to Pedro Campaña it was possible to analyse the surface
crust separately from the bulk of the paint layer. The proportion of calcium oxalate was greater in
the crust, as would be expected since it is likely to originate from interaction with dirt.

FTIR microscopy of a series of artificially aged paint samples of smalt helped to interpret and
understand the results from the paintings. In the spectrum of a test film which had had the
equivalent of around 100 years of aging a peak was present at around 1560 cm-1, showing that
potassium soaps had formed; this peak was absent in a spectrum of an unaged control sample. A test
sample of smalt in linseed oil which had been painted out in 1964 and left to age naturally, and
which had become very brown and dirty, was also analysed. In this sample, as well as the expected
potassium soap band at around 1560 cm-1, bands at around 1640 cm-1 and 1320 cm-1 which can be
ascribed to calcium oxalate were also present; this is very similar to what was seen in FTIR spectra
of real paint samples. Two of the amide bands of a protein also occur at around 1640 and 1560 cm-1,
so if both oxalate and potassium soap are present together, as they are in degraded smalt oil paint,
these might mistakenly be taken as an indication that protein is present. The FTIR results from test
samples are therefore important in clarifying the assignment of the bands. This is particularly
significant because some historical documentary sources suggest grinding smalt or other blues in
egg yolk or glue before grinding with drying oil, to improve the working properties.

This study of degraded smalt in oil from a number of National Gallery paintings has confirmed that
potassium is leached from the pigment. It has also shown that soaps and salts are formed in the
medium surrounding the pigment particles, and that migration to the surface of the paint creates
crusts similar to those found on degraded vessel glass that can be further modified by reaction with
the environment. Although a crust can often be seen on the surface of degraded smalt paint, it has
tended to be dismissed as an unrelated accretion such as dirt or old varnish. These observations help
to understand the nature and behaviour of the surface crust, and to appreciate that it is closely linked
with the deterioration of the pigment, which is important when considering cleaning or conservation
of a painting, as is the fact that water soluble potassium soap is produced on degradation. In
addition, the loss of a large amount of alkali, which can alter the surface of the smalt glass particles
and change the nature of the pigment–medium interface, as well as the formation of salts in the
paint, could disrupt the physical integrity of the paint film itself, and may begin to explain the
blanched and disintegrated appearance of discoloured smalt in oil paintings.

References

1. H. Paschinger and H. Richard, ‘Blaupigmente der Renaissance und Barockzeit in Österreich’,

Naturwissenschaften in der Kunst, Vienna 1995, pp. 63–6.
2. M. Spring, N. Penny, R. White and M. Wyld, ‘Colour Change in The Conversion of the
Magdalen attributed to Pedro Campaña’, National Gallery Technical Bulletin, 22, 2001, pp. 54–63.
3. J.J. Boon, K. Keune, J. van der Weerd, M. Geldof and J.R.J. van Asperen de Boer, ‘Imaging
microspectroscopic secondary ion mass spectrometric and electron microscopic studies on
discoloured and partially discoloured smalt in cross-sections of 16th century paintings’, Chimia, 55,
2001, pp. 952–60.
4. M. Spring, C. Higgitt and D. Saunders, ‘Investigation of Pigment-Medium Interaction Processes
in Oil Paint containing Degraded Smalt’, National Gallery Technical Bulletin, 26, 2005, pp. 56–70.