Maney Publishing

FTIR Studies of the Effects of Pigments on the Aging of Oil

Author(s): Jaap van der Weerd, Annelies van Loon and Jaap J. Boon
Source: Studies in Conservation, Vol. 50, No. 1 (2005), pp. 3-22
Published by: Maney Publishing on behalf of the International Institute for Conservation of
Historic and Artistic Works
Stable URL: http://www.jstor.org/stable/25487713
Accessed: 03-02-2016 12:12 UTC

REFERENCES
Linked references are available on JSTOR for this article:
http://www.jstor.org/stable/25487713?seq=1&cid=pdf-reference#references_tab_contents

You may need to log in to JSTOR to access the linked references.

Your use of the JSTOR archive indicates your acceptance of the Terms & Conditions of Use, available at http://www.jstor.org/page/
info/about/policies/terms.jsp

JSTOR is a not-for-profit service that helps scholars, researchers, and students discover, use, and build upon a wide range of content
in a trusted digital archive. We use information technology and tools to increase productivity and facilitate new forms of scholarship.
For more information about JSTOR, please contact support@jstor.org.

Maney Publishing and International Institute for Conservation of Historic and Artistic Works are collaborating with
JSTOR to digitize, preserve and extend access to Studies in Conservation.

http://www.jstor.org

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
FTIR Studies of the Effects of Pigments
on the Aging of Oil

Jaap van derWeerd, Annelies van Loon and Jaap J.Boon

as a result on the
This study describes the changes in the infrared spectra of oil paint of aging. The focus is influence ofpigments
on the in the oil medium. Several made with were
long-term changes binding naturally aged paints differentpigments analysed
most
using Fourier-transform infrared spectroscopy (FTIR). One of the pronounced effects observed in the infrared spectra of aging
paint is the shifting and broadening of the carbonyl band due to theformation ofcarboxylic acids. Another effect ofpigments on
the oil binding medium is the catalysis of the hydrolysis of triglyc?rides, as indicated by the decreasing intensity of the ester
the nature a on the CH
absorption. Finally, of thepigment included has profound effect stretch absorptions. From these results it
is clear that pigments can significantly alter the infrared spectra of drying oil, and should therefore be identified to ensure the correct
assessment
of the infrared spectra in drying oil paint.

INTRODUCTION have been performed using chemically pure esterified

fatty acids, instead of the triglyc?rides that make up
Oil is a natural product that can be pressed out of a
normal drying oil. Furthermore, the time-scale of most
variety of plant seeds. Some types of oils, e.g., linseed, chemical studies is very short; the changes on a
or to form a solid longer
walnut poppyseed oil, dry chemically time-scale are simulated or
by using thermally- light
to air. These so-called
upon exposure drying oils have accelerated the assumption
aging [5, 10-13]. However,
when used as a
good working properties binding that this accelerated not
aging does change the aging
medium in paint [1, 2]. These properties made vegetable
processes is not easily verified. The most important
drying oils the common binding medium in paints from
restriction of the majority of aging studies is the absence
the fifteenth to the twentieth century, when they were of pigment, which is a crucial and potentially reactive
mostly replaced by alkyd and acrylic media.
compound in paint. The presence of pigments or other
Thedrying of oil has been investigated thoroughly additives might very well influence the aging process of
over the past 130 years, and a detailed of the
description on
paint. This long-term influence of pigments paint has
mechanisms involved can be found in the literature
[3? on a
long been recognized macroscopic level [14], but
9]. It appears to be a very complicated process, in which
the underlying is
chemistry largely unknown.
a number of different mechanisms are simul
occurring This an infrared on
study presents spectroscopic
study
taneously. However, it is not clear to what extent the
aged oil paints. Infrared spectroscopy has proved to be a
models are a valid of a normal
developed description
very useful tool in the analysis of the drying process of
aging paint, as important differences exist between paint oil and the investigation of traditional paints. A mechan
and the model which were to
compounds investigated ism of early reactions in the
drying of oil is presented
formulate the mechanisms. Most of the drying studies
and illustrated by a study in which the effects of the
on the infrared spectra are followed in a time
drying
ReceivedDecember2002, revised
July 2004 resolved series of measurements. Subsequently, infrared

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
4 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

an free radical is not consumed

spectra of several traditionally made and naturally aged adjacent fatty acid. The
are and discussed. the attachment, and the process might repeat
paints presented during
itself, leading to a higher molecular weight fraction.
Addition of a free radical to a double bond in the same
MECHANISM OF THE DRYING PROCESS
fatty acid leads to intramolecular cyclization [15]. How
1 presents a of the reactions ever, these reactions are slow, and
Figure simplified model that only take place when
take place during the chemical drying of oil. The initial the oil is heated in the absence of oxygen, e.g., during
process in the drying of oil is the formation of free the anaerobic heat-bodying of oil [6]. The formation of
is possible of a hydrogen bonds is thought to be rare in the pres
radicals. This by elimination carbon-carbon
atom from an unsaturated ence In this case, addition
fatty acid. The formation of of oxygen. of oxygen usually
reactive free radicals is energetically unfavourable, and leads to the formation of peroxides. The hydroperoxide
occurs when the radical formed can be stabilized binds to one of the terminal atoms of the
only normally
resonance in the formation of
by [3, 6?8]. This stabilization is possible when delocalized radical, resulting
the hydrogen is removed from a m?thyl?ne group on an energetically favourable conjugated double bonds [16].
a
OC-position to double bond, or from am?thyl?ne group The free peroxyl radical (ROO*) can react with another
between two unsaturations. The latter case is shown as free radical and so leads to dimerization of two fatty
the initial reaction in Figure 1. acids. However, a more is the addition of
likely process
are a to the a
The radicals formed effectively trapped by anti hydrogen atom, leading formation of
oxidants that are naturally in of oxygen to an unsaturated
present drying oil. Trap hydroperoxide. Addition
can result in a shift of one of the double
ping of radicals inhibits the drying of oils, but deactivates fatty acid bonds
the antioxidant. The of oil does not start until from the original position. The newly formed double
drying
this deactivation process is complete. The delocalized bond is normally in a ira?5-configuration. Furthermore,
radical can in principle attach itself to a double bond in the addition of oxygen enables the free rotation around

H?
a,CH3

T Degradatior

jj Polymerisation

Figure 1 Simplifiedmodel of the early reactions takingplace during thedrying of oil. This scheme is based on themechanisms presented by
Wexler [6] and Porter [7, 8].

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIR STUDIES OF THE EFFECTS OF PIGMENTS ON THE AGING OF OIL 5

the C-C bond to the attached as solids, but do not yield very specific informa
adjacent peroxide, investigate
is no resonance. Elimina tion on the network. Size exclusion
rotation longer restricted by chromatography
tion of oxygen after rotation of the C-C bond results in (SEC) and massspectrometry using soft ionization
a transformation of the original eis double bond into an techniques recently enabled the observation of isolated

energetically favourable trans double bond [8, 10]. oligomers up to hexamers [4], but an accurate descrip
Addition and elimination of oxygen can occur several tion of the higher molecular weight fraction is a chal
times and lead to a more or less transformation lenge for future research.
complete
of the eis to trans double bonds. Meanwhile, analysis of the smaller molecules present
formed addition are not in aged oils has proved very informative. Several
Hydroperoxides by oxygen
stable and will be cleaved in the course of time. This researchers isolated the soluble fraction from aged paint
results in the formation of free radicals. by solvent extractions. These extractions have been used
cleavage again
Both peroxyl (ROO?) and alkoxy (RO#) radicals can be to identify the
drying oil and its preparation method [19,
formed in this process, the latter being shown in Figure 20]. Extractions have also been applied in the sample
1. These radicals give rise to different types of reactions, for infrared spectroscopy, to avoid
preparation mainly
i.e., polymerization, termination or reac the disturbing influence of [20].
degradation inorganic pigments
tions, as shown in Figure 1. In a polymerization reaction, Extractions are combined with chemical
normally
a nearby double bond is attacked and the corresponding derivatization to improve the volatility of the
techniques
linked to the fatty acid where extracted material. Van den Berg et al. used
fatty acid is chemically the Recently,
radical was present. Reaction with a double bond in the an two-step derivatization to determine the
elegant
same to the formation or
fatty acid leads of epoxides degree of hydrolysis of the ester bond between the fatty
structures. A more is the con acids and glycerol [21]. It appeared that hydrolysis is a
larger ring regular pathway
densation of two radicals, which consumes the radicals. slow process (some decades) to the
relatively compared
A further important reaction that can be caused by a free initial drying of oil.
radical is the degradation of the fatty acid on which the It is generally that the role of pigments
assumed in
radical resides. This process leads to the formation of the initial of drying
stages is catalytic or inhibitive,
and or the breakdown
smaller alcohols aldehydes [17], which eventually influencing the activation of oxygen
oxidize to volatile acids. These small mole of hydroperoxides However, there are indications
carboxylic [22].
cules might act as and their evaporation might that several pigments undergo chemical alteration
plasticizers during
a part in the of the paint. the aging of paint. Discoloration of the paint is the most
accordingly play hardening
The several mechanisms that play a role in aging of obvious indication of such a process. Another indication
oil paint are certainly more complicated than can be is the physical change of the paint layer to a hardened,

explained in a single figure. Figure 1 therefore focuses brittle system. This hardened system has been described
on the most aspects. This the as a network, in which the several carb
general figure ignores poly-anionic
presence of different
types of fatty acids, the important oxylic acid groups are stabilized by metal ions [23]. Pig
role of catalysts in the different steps, the eis?trans ments are the most source of these metal ions.
probable
transformations as a result of successive oxygen addi studies on the long-term behaviour of
Unfortunately,
tions, the role of photoxidation in the formation of artists' in paint are scarce. Rasti and Scott
pigments
hydroperoxides [16], and the several other reactions that quantified oxygen absorption, weight loss, hydroperoxide
take place on of oil the and degradation in paint films with
heat-bodying [18]. However, formation, products
cited provide a detailed overview of these different
publications pigments [13]. Vermilion-pigmented paint
effects. In general, the research carried out
during the films showed a loss, high hydro
relatively high weight
past 130 years has resulted in an accurate description of concentration, and high relative amounts of
peroxide
the possible reaction pathways. The main hiatus in the degradation products. Surprisingly, metal-containing
analysis of dried oils is the accurate description of the pigments like lead white and verdigris were found to

polymer network. This fraction is normally insoluble have an inhibiting effect on

these phenomena. It is likely
and non-volatile, which the separation and that at least part of the results can be explained
complicates by the
of intact molecules by methods such as gas rather untraditional in these experiments
investigation samples used
chromatography, liquid chromatography and mass (1% w/w mixtures of pigment in oil, layer thickness
?
spectrometry. Other
analytical techniques infrared 2 mm, UV illumination The effect of lead
aging).
spectroscopy, differential scanning calorimetry (DSC), white, be reduced and
especially, might by scattering
?
Raman spectroscopy can be to of the UV
applied directly absorption light.

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 6 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

Meilunas et al. have compared spectra of fresh paint been

previously investigated by gas chromatography?
a similar mass
with paint after accelerated aging, and with 50 spectrometry (GC-MS) [21].
on test This article provides a
year-old paint panels [10].
overview of the changes in infrared spectra upon
good
EXPERIMENTAL
aging of linseed oil and lead white-pigmented linseed
oil. It shows several indications for the influence of the
Samples
on the mechanism. to
pigment aging According
was on a
Meilunas et al., the presence of lead reduces the number The drying of oil study performed cold-pressed
of ester linseed oil, to which 0.06% cobalt was added as a
groups by catalysis of the hydrolysis. Instead,
metal carboxylates
were observed. Luxan and Dorrego catalyst.The oil was prepared byWim Muizebelt (FOM
[11] investigated the reactivity of several pigments to AMOLF). Old linseed oil thathad been kept in a closed
under unrealistic vial was taken from a painting materials collection about
form metal carboxylates aging condi
tions. However, their study seems to be based on poorly 50 years old, which to a sales representative of
belonged
founded It is presumed, for example, that Sikkens, a Dutch manufacturer, and was
presumptions. paint kindly
metals can the drying of oil in the form of provided by Martin Paans. The naturally aged linseed oil
catalyse
only
metal metal are were taken from various collections. Paints
soaps. Furthermore, carboxylates paints
assumed to be soluble, as the spectra are recorded from containing vermilion, iron oxide, ultramarine, indigo
solvent extracts. and lead white were taken from the Von Imhoff collec

tion, which was von Imhoff in 1973

This small number of studies clearly indicates that prepared by H.C.
have an influence on the long-term with cold-pressed linseed oil (Miihlfellner-Rupf,
pigments aging
the results are not complete, Z?rich, The oil was allowed to stand in
process of paint. However, Switzerland).
and are sometimes even One of these flat dishes 4 mm in height for three weeks, after which
contradictory.
contradictions concerns the catalytic behaviour of lead the skin was removed. The oil was mixed with pigments

on et al. conclude that until a workable was obtained. The different paints
white the drying of oil. Meilunas paint
acts as a catalyst were on limewood and hung
lead white [10], while Rasti and Scott applied primed panels
indicate that lead white inhibits aging [13]. The under natural light conditions in the Canadian Con

due to a servation Institute Ottawa). The were

contradictory results might very well be (CCI, samples
different aging procedure by followed these authors: carefully scraped off the paint layer. Paints containing
et al. investigated cadmium red, red lead, Naples ochre,
Meilunas thermally and naturally aged yellow, yellow
and Scott used UV illumination for gold ochre, green earth, Kassel earth, zinc white and
samples, while Rasti
accelerated It is known that lead white lead white were taken from the Doerner collection. The
aging. efficiently
test were made 1912
light [24] and thisabsorption is amore likely
in this collection between
absorbsUV panels
and 1941. The test panels (until 1938) were made
explanation for the inhibiting effect than any chemical early
Professor Alexander Eibner. Later were
effect. The controversy illustrates the fact that the aging by panels
his The were
may significantly influence the chemical aging produced by (former) pupils. paints
procedure
stored under normal conditions but were found
of the paint in a complex way. initially
in a closed cupboard when the samples were taken. An
overview of the paints analysed is presented in Table 1.
OUTLINE OF THE CURRENT STUDY

This study presents the infrared spectra of several aged

Experiments
in order to investigate further the long-term
paints
in paint. were The fluid were on a zinc selenide (ZnSe)
changes Only naturally aged paints samples applied
to minimize the bias due to the aging disc for infrared transmission experiments. The solid
investigated,
method. Furthermore, the composition of these paints is were in a P/N 2550 diamond cell
paints squeezed
were taken from before measurement.
typical of traditional paints. The paints (Graseby Specac, Orpington, UK)
various collectionsof test panels. The test panels in the The FTIR were a Bio
spectra presented acquired using
Von Imhoff collection are 30 years old. Still older recon Rad FTS-6000 FTIR spectrometer (currently
Digilab,
structions are obtained from the Doerner collection, Mass., USA), connected to an IR micro
Cambridge,
which contains a number of 60-year-old test as UMA-500) and a MCT detector.
panels scope (Bio-Rad
well as some 80-year-old test panels. The oil medium in The resulting spectra were processed using the Bio

several from the Von Imhoff collection has Rad Win-IR Pro software. Baseline correction and
aged paints

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIRSTUDIES OF THE EFFECTS OF PIGMENTSON THE AGINGOF OIL 7

Table 1 Overview of the aged paints investigated in thisstudy is stored for each of these periods. Selected
spectrum

Pigment Colour index Source3 Year Oil Support Fig spectra of this series were processed using Matlab 5.2
to form
(The Mathworks Inc., Natick, Mass., USA)
Vermilion PR106 1973 Linseed Panel 5
Figures 3A and B. Figure 22 compares the height and area
Cadmium red PR108 1937 Linseed Panel 6
Ironoxide PR101 1973 Linseed Panel 7 of the peak around 2930 cm-1 in all of the spectra
Red lead PR105 1916 Poppy Canvas 8 in Figures 5-21. The values presented for
presented
Naples yellow PY41 1939 Linseed Canvas 9 area were calculated the Win-IR Pro
height and using
Yellow ochre PY43 1939 Linseed Canvas 10
software. The (all values
definitions in cm"
Gold ochre PY43 1939 Linseed Canvas 11 applied peak
Green earth PG23 1939 Linseed Canvas 12 1) are as follows. Height of peak: baseline (3030, 2800),
Canvas b centre: extreme in region Area of peak:
Kassel earth Natural 1973 Linseed (2970, 2910).
Brown 8 1939 Linseed Panel baseline (3030, 2800), edges (2968, 2901), centre
Ultramarine PB29 1973 Linseed Panel of some
irrelevant. X-ray diffraction (XRD) data pig
Indigo Vat blue 1 1973 Linseed Panel
ments were made available by I.N.M. Wainwright (CCI).
Zinc white PW4 1941 Linseed Panel
Lead white PW1 1912 Linseed Panel
1941 Linseed Panel
1941 Linseed Panel
RESULTS
1941 Linseed Panel
1973 Linseed Panel Early reactions during thedrying of oil

(a) The paints were taken from the collections prepared by H.C. von
The dryingof oil was monitored by FTIR to study the
Imhoff(I) or from the collection kept at theDoerner-lnstitut (D). mechanisms involved. A thin film of oil was applied
to
(b) Results not shown. an infrared transparent disc to enable transmission FTIR
measurements and to improve the oxygen supply via
subtraction of a water vapour spectrum were
applied
to diffusion. An infrared spectrum of the fresh linseed oil is

improve the spectral quality. Every scaling mark on

the displayed in Figure 2. The various absorption peaks in
vertical axes in 5?21 was set to 0.2 absorbance this spectrum are assigned in Table 2. Subsequently, the
Figures
units, to allow an easy comparison of the absolute value film was analysed at fixed time-intervals. Selected spectra
of the spectra. The of the from the data-set obtained in this way are
in
apparent spectral resolution presented
FTIR spectra was increased by taking the second deriva Figures 3A and B. These
figures only display selected
tive of the spectra [25]. The use of spectral deconvolu parts of the spectra to visualize the changes more clearly.
tion [26] was thought inappropriate
as the results
depend The time passed since the start of the experiment is
on user-selectable parameters. The second on the left side of the spectra.
indicated
significantly
derivative spectra were inverted to make the absorption Theleft part of the spectrum in the fresh oil is

peaks positive. Infrared spectra of oil during the drying dominated by a series of aliphatic vibrations around 3000
were
process acquired using the kinetics mode, cm1, caused by the large amount of
CH2
and
CH3
embedded in the Win-IR Pro software. In this mode, groups in the fatty acids. Stretch vibration of CH bonds
the spectrometer measures The spectra are lead to high absorptions at 2926 and 2855 cm-1 with a
continuously.
averaged during periods of 10 minutes and a single shoulder at 2958 cm-1. Bending vibrations of these

4000 3500 3000 2500 2000 1500 1000

Wavenumber

Figure 2 Infraredspectrum of fresh linseed oil.

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
8 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

Table 2 Assignment of the absorption bands in the spectrum of moieties are present at 1460 and 1374 cm-1
(CH3).
fresh linseed oil (shown inFigure 2)
These not show much variation in time. On
peaks do
Wavenumber (cm"1) Moiety Source the other hand, the smaller peak at 3009 cm-1, assigned
to the a'5-type unsaturated CH group (C=C-H) [27],
3009 C=C-H (eis) stretch Fatty acid
in about five hours. The same group absorbs
2958(s) CH3 stretch Fatty acid disappears
2926 CH2 stretch Fatty acid at 726 cm-1, and the intensity of this peak also decreases.
2855 CH2 stretch Fatty acid The simultaneous increase of the absorption at 980 cm-1
1744 C=0 Ester bond
suggests that the eis double bonds are isomerized to trans
1653 C=C Fatty acid
[28, 29]. The presence of unsaturations
1460 CH3 (asymm. bend) Fatty acid configuration
also leads to the small at 1653 cm-1, caused
CH2 (scissors) peak by
1374 CH3 (umbrellamode) Fatty acid C=C double bonds in the fatty acids.
1238 C-0 Ester bond
Another clearly changing feature on the left-hand side
1163 C-O Ester bond
of the infrared spectrum is the formation of a new
1099 C-0 Ester bond
720 band at 3400 cm-1. The and
CH2 rock Fatty acid absorption spectral position
726 C=C-H (eis) bend Fatty acid broad appearance of this band indicate that it should be
to alcohol and/or vibrations,
assigned hydroperoxide
both of oxidation. A further distinction
products
between alcohols and hydroperoxides cannot be made,
as the difference in their peak maxima is small. Discrim
ination only becomes possible after specific derivatiza
tion of the oil [5, 30, 31]. The studies cited have
indicated that hydroperoxides formed in the early stages
are and ethers. The
subsequently replaced by alcohols
spectrum in 3A shows an increased
uppermost Figure
absorption in the spectral region 3000-3200 cm-1
the peaks at 2926 and 3400, arrow in Figure
(between
are caused
3A). These absorptions probably by carb
acid moieties, as is confirmed the appearance
oxylic by
of an absorption band at 1414 cm-1 and the broadening
of the carbonyl band. This intense carbonyl peak at 1744
cm-1 is originally due to ester bonds between glycerol
and fatty acids. The acid at about
carboxylic absorption
1710 cm"' is normally not resolved from this peak and

partly explains the broadening [10, 29]. The formation

of carboxylic acids is a generally recognized degradation
reaction in drying oil, and the associated increase of the

acidity is confirmed by titration studies [32]. However,

other types of carbonyls, e.g., ketones,
aldehydes,
lactones and anhydrides, might also play a role in the
observed broadening of the carbonyl band.
The drying studies presented in Figures 3A and B
show the extensive changes of the infrared spectra of oil
upon drying. Infrared spectroscopy has accordingly been
one of the most in the elucidation
important techniques
1400 1200 1000
of the mechanism shown in Figure 1.
Wavenumber
(cm1)

Infraredspectra of unpigmented aged oils

Figure 3 FTIR study of thedrying of linseed oil, showing the infrared
spectra of linseed oil at differentperiods after itsapplication as a thin
film.The timesince application is indicated on the leftside of the Figure 4
shows spectra of two different unpigmented
oil These a reference for the
spectra. (A) Spectral region 2600-3600 cm~\ (B) Spectral region 700 aged samples. provide
1800 cm-1. spectra of various pigmented paints presented in the next

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIRSTUDIES OF THE EFFECTS OF PIGMENTSON THE AGINGOF OIL 9

dilaurin (SDBS refs34789 and 7719, IntegratedSpectral

Data Base System for Organic Compounds, www.aist.

go.jp/RIODB/SDBS/menu-e.html). Similar mole

cules, i.e., can also be formed due to

diacylglycerols,
hydrolysis. However, the presence of a fatty acid impur
seems a
ity in the samples measured for this database
more for the absorption at 1712 cm"1
likely explanation
than an absorption by diacylglycerols.
An absorption at about 1710 cm-1 is also present in the

upper spectrum in Figure 4 and the spectrum provided

by Meilunas et al. However, in these cases it is poorly

1000 resolved from the absorption at 1740 cm"1, and is only

4000 3500 3000 2500 2000 1500
Wavenumber visible as a shoulder. A similar loss of resolution is seen
in the CH stretch vibration seem narrower
peaks, which
Figure 4 Infraredspectra of aged, unpigmented linseed oil. (A)
in spectrum B than in spectrum A (Figure 4). The broad
Ninety hours after application as a thinfilm.(B) Fiftyyears after
seems to be
production. This oil has been kept ina closed container. ening typical of natural aging, and spectrum
A is therefore considered the better reference for the spec
section. The aim of this comparison is the evaluation of tra of the pigmented films presented in the next section.
on the
the influence of pigments aging of oil. Spectrum
A a thin linseed oil
represents layer cured for 90 hours INFRARED SPECTROSCOPY OF NATURALLY
to the uppermost in Figures 3A and B).
(equal spectrum AGED OIL PAINTS
This spectrum is remarkably similar to the spectrum of
the 50-year-old oil film Several were In Figures
unpigmented presented by naturally aged paints analysed.
Meilunas et al. [10]. This suggests that the crosslinked 5-21, the figures on the left show the normal infrared
oil is relatively stable after an initial drying their second order derivatives are
system spectra: partly (700
at least as far as can 1800 cm"1) shown in the figures on the right. Table 1
period, be observed by infrared
The claim that a thermal treatment (24 an overview of the pigments included. Their
spectroscopy. provides
hours at 120?C) the infrared spectra, as well as the second derivatives of these
faithfully reproduces spectral
of a 50-year-old are in Figures 5-21 and discussed in
features naturally aged paint [10] should spectra, presented
therefore be taken with a of salt, as it also the following sections.
pinch
a a
reproduces paint with drying time of just 90 hours
after an initial period of only a few days. The lower
Vermilionpaint
in Figure 4 represents a stand oil,
spectrum 50-year-old
which was taken from the promotional material of a sales The spectrum of a 30-year-old vermilion-containing
representative of a Dutch paint manufacturer. This oil paint is shown in Figure 5. The corresponding second
a closed most to the
has been kept in container during of its derivative spectrum is displayed right of this
lifetime, and was as a thin film at the time spectrum. Vermilion does not absorb in the MIR (mid
only prepared
of the infrared measurement. Therefore, the oxygen infrared) region, but causes extensive scattering. The

supply
to this oil has been restricted, and a low amount intensity of the transmitted light therefore decreases with
of oxidation is expected. Absorption peaks of oxidation the decreasing wavelength. The corresponding slope in
are indeed small at 3440 cm-1, C-O the baseline was removed a baseline correction, but
products (OH by
at 900-1400 The ester at 1740 the low transmittance causes a low ratio
background cm'1). peak signal-to-noise
cm-1 is accompanied by
a distinct
peak
at 1712 cm-1. (S/N) on the left side of the spectrum. Vermilion does
These are to fatty acids formed by hydrolysis of not seem to induce the formation of detectable amounts
assigned
the esters, because acid formation due to of products that are not present in unpigmented aged
glycerol
as shown in Figure 1, is limited by the as its spectrum resembles spectrum A in
degradation, paint, closely
oxygen Indications for this are the relatively low Figure 4. The carbonyl moieties lead to a broad absorp
supply.
of the ester band at 1740 cm-1 and the tion at 1734 cm"1 (1744 cm"1 in fresh oil, Figure 2).
intensity
deformation of the ester triplet (-1246, 1174 and 1110 the spectral resolution means of the second
Increasing by
at -1712 cm-1 is also seen in library derivative reveals the presence of clearly
cm-1). The peak spectrum
spectra of glycerol-l,2-distearate and glycerol-1,3 distinct carbonyl peaks (1740, 1708, and a smaller

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
10 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

jjr^H. Ljj?
&
3500 3000 2500 2000 1500 1000 500 1700 1500 700

Figure 5 Vermilion.

at at as
absorption 1781 cm-1). The clear triplet of peaks pigment, they are also found in pure iron oxide
1247, 1183 and 1102 cm-1 in the raw spectrum shows pigment used in this test panel. The at 1177
absorption
the presence of intact esters in the dried oil. cm"1 is not due to this pigment, and should be assigned
to ester groups. The presence of esters is confirmed by
the carbonyl at 1738 cm"1 deriva
Cadmium red paint absorption (second
tive). Carbonyl at 1708 and 1782 cm"1
absorptions
The infrared spectrum of a 60-year-old cadmium red (second derivative spectrum) have in the
appeared
is presented in Figure 6. CdS does not absorb spectrum. The
paint intensity of the 1708 cm"1 peak is rela
infrared light, and the scattering is low compared to
tively high and this explains the low wavenumber of the
vermilion. Therefore, the S/N on the left side of the in the raw
carbonyl absorption spectrum (1720 cm"1).
spectrum is higher. Otherwise, the spectrum is very The at 3200-2500, 1413 and 921 cm"1 indi
absorptions
similar to that of vermilion paint. Even the carbonyl cate that the 1708 cm-1 should be assigned to carb
peak
absorption pattern observed in the second derivative acids. The abundant presence of carboxylic acids
oxylic
spectra (1782, 1739 and 1707 cm-1) is very similar. This in this paint is confirmed mass spectrometry
by [21].
cadmium red is therefore concluded not to have had a

great influence on the drying paint. Minium (red lead) paint

The main features in the spectrum of the minium

Iron oxide paint
containing paint in Figure 8 are peaks at 1177/1117,
The absorption spectrum of an iron oxide-containing 1090 (truncated in this figure) and 984 cm"1. The
peaks
paint is displayed in Figure 7. This spectrum is clearly 1185, 1123, 1072 and 984 (see second derivative) ex
different from the spectra of vermilion and cadmium red actly coincide with the absorptions of ref
BaS04 (SDBS
as it shows a strong at 1100 cm-1 as The presence of Ba has been confirmed by EDX,
paint, absorption 40201).
well as an at the but the source of BaSO, It can be due to
absorption right side of the spectrum is not known.

(<700 cm-1). These can be to the an of the red lead or a

absorptions assigned imperfect sampling paint layer

3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 6 Cadmium red.

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIR STUDIES OF THE EFFECTS OF PIGMENTS ON THE AGING OF OIL 11

3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 7 Ironoxide.

3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 8 Red lead.

filler introduced with the pigment. The relatively strong (Figures 8 and 9) show that pigments that mediate the

peaks
at 1526 and 1404 cm"1 can be attributed to lead formation of metal carboxylates simultaneously reduce

soaps [29]. The intensityof the carbonyl peak at 1741 the number of carboxylic acids, which can
readily be
cm"1 is lower than the C-H stretch vibration at 2924 cm"1, explained by the consumption of carboxylic acids during
unlike the pigmented so far. The
paints discussed minute the formation of metal carboxylates.
at 1707 cm"1 in the second derivative spectrum
absorption
shows the near absence of carboxylic acids. The absence
Yellow ochre paint
of carboxylic acids is confirmed at
by the low intensities
-3200-2600 cm"1 (raw spectrum), and 1414 cm"1. The absorptions of ochre dominate the infrared spec
trum of a 65-year-old yellow ochre paint. The most
features 10) are the intense
pronounced (Figure
Naples yellow paint
(truncated) silicate absorptions at 1200-980 cm-1, 918,
The infrared spectrum of an 806 and 701 cm-1. The presence of quartz in these
aged paint containing
Naples yellow is presented in Figure 9. This spectrum has been shown XRD. Water in the
samples by crystal
at 1548 and 1413 cm"1, which are
shows strong peaks lattice of the pigment gives rise to the sharp peaks at
not present in the spectrum of the pure 3695 and 3619 cm-1 and might also contribute to the
pigment
before
[33]). They are to metal at about 1622
cm"1. Finally, the characteristic
(reported assigned absorptions
carboxylates that were formed during aging. The absorption pattern between 2600 and 3500 cm-1 is partly

presence of intact ester bonds is indicated by the glycerol assigned to hydroxyl groups in or on the pigment
ester as the observed
triplet at 1251, 1178 and 1099 cm"1. The second particles, maximum (as low as 3114 cm"1)
derivative shows that the is uncommon for organic materials.
spectrum carbonyl peak mainly The aliphatic moie
consists of ester absorption at 1741 cm"1 with a ties in this lead to broad bands at
only sample absorption
small contribution of carboxylic acids at 1707 cm"1. 2944, 2864, 1453 and 1382 cm-1. The carbonyl absorptions
Both red lead and Naples yellow pigmented paints (1724 cm-1) are resolved by the second derivatization in

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
12 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

Li
3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 9 Naples yellow.

>_. +?J H
3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 10 Yellow ochre.

at 1738 and 1705 cm"1. Unfortunately, the ester The materials mask many of the
peaks biguous. inorganic
triplet around 1170 cm-1 is completely masked by the organic features in the spectrum. The remaining organic
as
strong Si-O absorptions. features include aliphatic peaks at 2938 and 2867 cm"1
well as 1464 cm"1 in the second derivative spectrum.
Gold ochre paint The second order derivatization again resolves the

carbonyl band into distinct absorptions at 1779, 1738

The spectrum of the aged linseed oil paint containing
and 1708 cm-1. The at 1624 cm"1 is well
absorption
gold ochre (Figure 11) is very similar to the spectrum resolved from the carbonyl peak (1717 cm"1), contrary
obtained from the yellow ochre. The second derivative
to the spectra of the 10
ochre-pigmented paints (Figures
spectrum shows a higher relative intensity of the 1707
and 11). The assignment of this peak (1624 cm"1) to
cm-1 carbonyl absorption. This intensity change led to
water in the crystalline lattice of the pigment (as sug
the significant shift of the carbonyl peak in the raw
gested in the discussion of the ochre paints) is contra
spectrum, from 1724 to 1710 cm"1.
dicted this spectrum, as the amount of water in the
by
crystal lattice of thispigment (3697 and 3619 cm"1) is
Green earth paint low. A better assignment might be the presence of
very
metal However, no further indications
The of green earth pigmented carboxylates.
spectrum paint film is
could be found to confirm this attribution.
presented in Figure 12. The green earth pigment used
in the reconstructions was found to contain silicates

(1039, 915, 801 cm-1)

containing water in the crystal Kassel earth (Van Dyke brown) paint
lattice (3697, 3619 cm-1), and calcium carbonate (2522,
1799 (small), 1416, 875 cm-1). Green earth reference The infrared spectrum 13) represents an
(Figure aged
spectra [34] are clearly different from the pigments in the paint prepared with Kassel earth, a sedimentary organic
test panel. The definition of green earth is not unam matter
consisting of fossil plant remains in the form of

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIRSTUDIES OF THE EFFECTS OF PIGMENTSON THE AGINGOF OIL 13

Figure 11 Gold ochre.

3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 12 Green earth.

or sub-bituminous coal
lignite [35]. The organic absorp oxylic acids is confirmed by absorptions at 3200-2600 and
tion at 1611 cm-1 is the most intense absorption in the at 1709 cm-1. In this spectrum clearly illustrates
particular,
infrared spectrum. This peak is caused by the pigment the increment in information that can be obtained after
itself, and has been to iron carboxyl second derivatization: two broad re
assigned tentatively peaks have been
ates [36]. Assignment to a or metal carb solved into a number of narrow absorptions.
carboxylate reproducibly
is confirmed by the presence of another broad a trace of can be observed as
oxylate Only inorganic materials
at 1416 cm-1, which can be to the a at 1099 cm"1. This is not
absorption assigned relatively sharp peak peak part
stretch. the of the glycerol as its
symmetric carboxylate Additionally, triplet, intensity is too high com
at 1611 cm-1 might be partly caused to the connected and 1240 cm"1).
absorption by pared peaks (~1170
aromatic structures, which are present in the Small amounts of glycerol esters are indicated, however,
abundantly
The at 1611 cm"1 has a very at 1736 cm"1 (second
pigment. absorption noisy by the modest absorption deriva

appearance in the second derivative spectrum. However, tive spectrum). The second
derivative of the carbonyl
structure at 1626,
the fine (including peaks 1567, 1587, peaks resolves the two absorptions (1736 and 1709 cm"1),
1608 and 1645 cm-1) is reproducible; the same but the resolution isworse than in other cases observed so

absorptions have been found in the Kassel earth far. This might very well be due to the presence of carb
taken from the Von Imhoff collection
pigmented paint onyl moieties in the Kassel earth pigment. Unfortunately,

(results not shown). These various should be the presence of the several related functional in
peaks groups
to different chemical of the the oil and pigment fraction makes a detailed evaluation
assigned surroundings
but a detailed identification of these of the oil fraction
carboxylates, impossible.
absorptions has not been established and is left for further
research. Second derivative of the broad
analysis absorp Ultramarine paint
tion band at 1416 cm-1 also reveals a number of underly

ing absorptions, including those at 1383 1464 The strongest in the spectrum of artificial
(CH3), absorption
and 1413 cm-1 (COOH). The of carb ultramarine
(CH,) presence pigmented paint (Figure 14) is the truncated

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
14 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 700
900

Figure 13 Kassel earth.

at 1001
silicate absorption cm-1 (SDBS, ref 3143). Other and 752 cm"1). These peaks mask most of the binding
are present at 714 and 680 cm-1. medium in the In fact, only the
pigment absorptions peaks fingerprint region.
due to the are rather
The absorptions binding medium carbonyl band (1728 cm"1) and the CH stretch vibrations
broad and featureless. In fact, the CH bend absorption (2940 and 2865 cm"1) can be assigned unambiguously.
(1466 cm-1) can be in the second Second order derivatization does not improve the
only distinguished
derivative spectrum. The broad CH stretch absorptions interpretation of the spectral data because indigo, being
have their maxima at 2945 and 2873 cm-1, compared to an aromatic structure, has many narrow
absorption
2926 and 2855 cm-1for the freshoil (see Figure 2). The bands. These sharp peaks
are
prominently present in the
exact of these absorptions appear to be very second derivative spectrum. The well-resolved bands for
positions
and values of the naturally vary be esters acids are
unstable, aged paints (1737 cm"1) and carboxylic (1707 cm"1)
tween 2924 (red lead in Figure 8) and 2945 (ultramarine seen as minor features in this spectrum.

paint in Figure 14). The shift to higher wavenumber

seems to accompany a broader appearance of the
normally Zinc white paint
[5]. A broad shoulder is present at 1641 cm-1. This
peaks
peak again gives the impression of a metal carboxylate, The spectrum of zinc white pigmented paint (Figure 16)
as it is a broad at 1414 cm-1. shows intense CH vibrational at 2933 and
accompanied by absorption peaks
2858 cm"1. The narrow
intensity of the carbonyl peak
(1740 cm"1) is lower than the CH stretch vibration at
Indigopaint
2933 cm"1, indicating that the amount of intact ester
The in the 35-year-old paint iswell pre bonds is relatively low. The second derivative spectrum
indigo pigment
as indicated acids by the negligible
served, by its intense blue colour. The many shows the absence of carboxylic
are clearly present in the spectrum in at 1709 cm"1. The clear and broad
indigo absorptions absorption carboxy
Figure 15 (3239, 3064, 1627, 1612, 1588, 1485, 1392, late absorption (1589 cm"1) consists of several separate
1321, 1300, 1200, 1173, 1130, 1077, 1014, 882, 861 peaks (second derivative, 1620, 1588, 1540 cm"1). The

3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 14 Ultramarine.

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIRSTUDIES OF THE EFFECTS OF PIGMENTSON THE AGINGOF OIL 15

3500 3000 2500 2000 500 1700

Figure 15 Indigo.

3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 16 Zinc white.

at 1460-1418 cm-1 resolves into the CH et al. test even

absorption peak Meilunas [10]. The Doerner series
as as
bend vibration (1467 cm-1) well peaks at 1415 and contains several lead white paints, with a number of
1376 cm-1. A minor addition of whiting to the different lead white types, oils, and additions. The infra
(CaC03)
zinc white is suggested by the combination of peaks at red spectrum of a paint prepared in 1912 is shown in
876 and 778 cm-1 (second derivative). The 1150 cm"1 Figure 17. Spectra of other paints from this series, made

absorption indicates the abundant of alcohol

presence in 1941, are shown in Figures 18?20. The lead white
in the oil. This peak is probably not due to a sili from the CCI test series is shown in
groups paint Figure 21.
cate or sulphate adulteration, as these moieties The most intense in spectrum 17 is due to
normally absorption
show a series of absorption bands in this spectral region. the carbonates present in the lead white pigment
lead a
Furthermore, sulphate impurities [37] would have (truncated, 1300?1450 cm"1). Less intense pigment
different maximum (1060 cm-1). The are seen at 3539 1048, 776
absorption assign absorptions (OH stretch),
ment to alcohols is confirmed the relatively strong and 681 cm"1. The at 838 cm-1 is due to
by absorption
at 3410 cm"1. The spectrum sug neutral lead carbonate which is a common
absorption presented (PbCO^),
that zinc white influences the aging of oil in differ of lead white most
gests component [24]. The intense organic
ent ways: it stimulates the formation of alcohol groups, features are present at 2933 and 2875 cm"1 (CH stretch)
catalyses the hydrolysis of glycerol esters, and forms and 1740 cm"1 (carbonyl). The second derivative of the
metal carboxylates with the carboxylic acids present. carbonyl region shows the presence of ester moieties at
1740 cm-1, but the almost complete absence of carboxylic
acids. The ester C-O 1248 and 1100 cm"1,
Lead white paint triplet (1169,
second derivativespectrum) confirms the presence of
Lead white is probably the most commonly used pig esters. The shoulder on the short wavelength side of the
ment in the history of painting. Therefore it has been intense carbonate band should be assigned to the
included in many test series, e.g., the painting of lead carboxylates
panel by absorption [10], but it ismasked by
Gettens, which has been analysed and reported by the adjacent very intense carbonate absorption.

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
16 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

C> (Ni o g 2b?

Fn l^%IMi^
3500 3000 2500 2000 1500 1000 500 1700 t?1500 1300 1100 900 700

Figure 17 Lead white (D1).

3500 3000 2500 2000 1500 1000 500 1700 1500 1300 1100 900 700

Figure 18 Lead white (D4).

CO j IM H

L-*I*-|?J fi*Jf\Nj(*~\rt
3500 3000 2500 2000 1500 1000 500 1700 1500 1300 900 1100 700

Figure 19 Lead white (D5).

Nevertheless, spectral subtraction of a pure lead white lead carboxylates. This attribution resembles the

spectrum revealed a clear at 1540 cm"1 (results attribution of the fine structure on the
absorption carboxylate
not shown). derivative in the Kassel
Second analysis of the absorption absorptionpeak earth-pigmented paint.
spectrum of lead white 17) reveals the However, the exact locations are different, as
paint (Figure spectral
presence of several small maxima
absorption (1533, another metal is involved. An even clearer fine pattern is
1628 seen
1543, 1551, cm"1). These
peaks look like noise, in the region between 1365 and 1480 cm-1 with
but their relevance is indicated
by their presence in the peaks at 1364, 1386, 1410, 1428, 1447, 1466 (CH
spectra of the other lead white-pigmented oil paints (see bend), 1474 and 1481 cm"1. All these small absorption
18?21). The several peaks in this region are appear in the various lead white that were
Figures peaks spectra
probably due to different coordination structures of the
investigated, which stresses their significance. The

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIRSTUDIES OF THE EFFECTS OF PIGMENTSON THE AGINGOF OIL 17

500 1700 700

Figure 20 Lead white (D6).

3500 3000 2500 2000 1500 1000 500 1700 1500

2&%
1300 1100 900 700

Figure 21 Lead white (CCI).

at 1410 cm-1 has been assigned to carboxylic white et al. are remarkable,
absorption paint reported by Meilunas
acids above. However, this seems not valid here, as
especially when the similarity of the spectra presented in
acids should rise to an band 17-21 is considered. The most
carboxylic give absorption Figures important
at 1707 cm"1, which is clearly not present. difference is the relatively low carbonate absorption in
A remarkable difference between the several lead the paint analysed by Meilunas et al., indicating that this
a much lower pigment concentration.
white-pigmented paint films is the different intensity paint has Indeed,
observed for the OH stretch vibration at -3535 cm"1. it is stated that the paint analysed was made of a 1:1
The intensity of this absorption varies in intensity be mixture of lead white and oil, which is lower than in
tween strong (Figures 17, 18, 21) and negligible (Figure traditionally prepared paint. The lower amount of lead
same are found for the OH white resulted in a higher amount of oxidation
19). The intensity differences products
at 3411 1715 as well as an
bend vibration (775-780 cm"1). The absence of these with absorptions and cm"1,

(3535 and 778 cm-1) correlates with the presence overall absorption increase in the
spectral region
peaks
of peaks at 838 and 2420 cm"1, and leads to a small shift between 1650 and 1000 cm"1. A further difference is the
in the intense lead white around 680 cm"1, better resolution of the peaks at 1622 and 1545 cm"1. It
absorption
to 678 is likely that these differences are caused
from 681 cm"1. These intensity changes and peak by the pigment
shift are the content of neutral lead concentration in the paint.
explained by
carbonate in lead white. Reference spectra ([24, 38] and
show that basic lead carbonate absorbs at 3535,
SDBS) DISCUSSION
778 and 681 cm"1, while neutral lead carbonate, which
is a normal constituent of lead white, absorbs at 2420 The large number of spectra that have been shown in this
cm"1. This indicates that of a classification of the different effects that pig
and 838 the composition study allow
lead white from different sources can be differ ments can have on the in oil. A number
markedly aging processes
ent, which is consistent with documentary
sources [39]. will be highlightedbelow. The broad
of characteristics
The differences between the spectra presented here ening of the carbonyl band, which had been observed in
and the results of the 50-year-old naturally aged lead a number of earlier studies, was shown to be due to the

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 18 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

formation of new carbonyl bands at 1705-1709 cm-1 and (vermilion, cadmium iron oxide,
red, yellow ochre,
around 1780 cm"1. The location of this triplet in which
the at 1707 cm-1 is
spectral gold ochre) absorption
appears to be very but the relative intens at 3200-2600, 1415 and
reproducible, accompanied by absorptions
ities are dependent on the
pigment present in the paint 915 cm-1 [29]. The mere absence of the 1707 cm"1 peak
?
film. Another effect that can be assigned to the presence in some of the metal soap-producing pigments
of pigments is the shiftof the CH absorption bands Naples yellow (Figure 9), lead white (Figures 17-21),
around 3000 cm"1. The most obvious effect observed in zinc white (Figure 16) and red lead (Figure 8), where
a number of paints is the formation of metal the carboxylic acids have reacted further to
carboxylates. obviously
?
metal carboxylates nicely confirms this assignment.
No indications were found for the presence of other
Carbonyl bands
groups that also absorb at ~1707 cm-1. Further
carbonyl
The carbonyl bands observed in the different spectra proof might be obtained chemical derivatization of
by
vary in peak width and position of the maximum aged paint material, e.g., using the method described

absorption.Both Meilunas et al. [10] andHartshorn [40] byMallegol et al. [5]. If the absorption at 1707 cm"1 is
have explained this by the formation of an extra, to be assigned exclusively to
carboxylic acids, it is
unresolved absorption peak at 1730-1700 cm"1 upon the remarkable that it is resolved from the ester absorption

drying of oil. Resolution enhancement through second (1740 cm"1) in only one of the spectra presented in the
derivative indicates that both effects are caused current study: the stand oil that has never been
spectra prepared
of extra absorptions at 1707 and 1780 as a
by the formation paint (spectrum B in Figure 4). In all other cases,
cm"1. These are well resolved in the second order the two carbonyl peaks were not resolved in the normal
peaks
derivative even when no shoulders or fine infrared spectra. This
spectrum, suggests that the extensive changes
structure can be seen in the raw spectra, e.g., in Figures that take place upon oil drying induce a broadening of
10-15. Furthermore, the carbonyl peak is not hindered the carbonyl peaks, obviously by the formation of

by masking due to absorptions of the common tradi several different chemical and physical environments for
tional pigments, which forms a major annoyance in the carbonyl groups.
traditional research FTIR. one of the The rather small at 1780 cm"1, which is ob
paint by Only peak
pigments investigated (Kassel earth) disturbed the served in most of the second derivative infrared spectra
of the oil in the has been to lactones or
analysis absorptions spectral region presented, assigned anhydrides.
between 1700 and 1800 cm"1. Therefore, this reproduc This absorption is thought to be specific for a drying oil
ible be useful in the classification of [10]. A further carbonyl at 1680 cm"1 is
triplet may very absorption
binding media. observed in the zinc white paint. This absorption has
The absorption at 1740 cm"1 can be assigned to esters been assigned to conjugated carbonyl groups [12].
[29, 41] that have been introduced in the paint as
triglyc?rides. This is confirmed by the presence of other
Metal carboxylates
ester peaks (1170, 1240, 1100 cm"1) whenever these are
not masked can be seen in the
by pigment absorptions (Figures 5-7, 9, 17 Several complex spectral differences
21). The intensity of this ester peak is variable, which region between 1650 and 1500 cm-1. Many of these can
must be to the number of remaining ester bonds be explained
related by the presence of metal carboxylates. The
in the paint. However, a of the spectra of carboxylates
thorough quantification absorption containing long-chain
an accurate of the and several metal ions have been
intensity would require determination fatty acids accurately
layer thickness and the pigment content, and is not reported [42]. The value reported for zinc carboxylates

straightforward. A general impression of the intensity of is ~1540 cm-1, and a small peak at 1540 cm"1 is indeed
the ester peak can be obtained by comparison with the found in the spectrum of zinc white paint (Figure 16).
asymmetric stretch vibration at -2930 cm""1. The However, the carboxylate at 1590 cm"1 is
CH2 absorption
quantitative accuracy of this approach is also question much more intense. The values reported for long-chain
as the of the CH stretch therefore not be correct for every type of
able, however, intensity fatty acids may
not be a number
vibration might linearly related to the amount of zinc carboxylate. Indeed, of selected reference

organic materials
(see discussion below). spectra illustrate that the nature of the carboxylic acid
The at ?1707 cm-1 has been to influences the characteristics of the
absorption assigned spectral absorption
the carboxylic acids which are formed upon oxidation. metal Zn-stearate and
carboxylate: palmitate (~1540 cm-1)
This seems to be confirmed
assignment by spectra [42], Zn-lactate (1597 cm"1) and Zn-oxalate (1631 cm"1)

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIR STUDIES OF THE EFFECTS OF PIGMENTS ON THE AGING OF OIL 19

(SDBS, refs3130, 12800 and 17155). A very interesting absorption peaks changes linearly with the height
for these is provided in the 22, see section for
comparison absorptions (Figure experimental parameters,
on are =
literature ionomers, which carboxylic acid R 0.99). The varying intensity of the oil seriously
formed by copolymeriza
containing polymers, normally complicates analysis of aged paint by FTIR.
quantitative
tion of ethene and methacrylic acid. Ionomers can be The absolute of the CH cannot be
intensity peaks
neutralized by metal ions [43], which form metal compared in the measurements
objectively reported
carboxylates with the carboxylic acids. Neutralization of here, as the exact amount of organic material in the light
ionomers with lead acetate has been reported to result in
path is unknown. Furthermore, these oil components
infrared absorptions at 1560 cm-1 [44]. In another have a extinction coefficient due to
study, decreasing hydro
ionomers have been neutralized by zinc oxide, which lysis (1740 cm"1) and oxidation (2924 cm-1). A valid
introduced infrared at 1624, 1585 and would an inert
absorptions quantitative analysis probably require
1538 cm"1. The relative intensities were found to be internal standard.
on the amount of water These considerations make an of the
dependent absorption [43, 45] assignment
and on the pressure applied to the
sample [46]. Hashi intensity to the loss of volatile material very
decreasing
moto et al. [46] mention that the different absorption The direct influence of hydrolysis or metal
unlikely.
bands can be related to different coordination states of formation can also be ruled out. This was
carboxylate
the carboxylic acids around the zinc atom, but a full confirmed measurements on ionomers, in which the
by
assignment has not yet been established. A of the CH stretch bands was found to obey
unfortunately intensity
better identification would not only lead to a better Lambert-Beer's law [47]. The origin of the hypso

understanding of ionomers but is expected to be chromic shift of the oil medium should
directly during aging
to aged paint, a system which is related to therefore be to oxidation and
applicable assigned possibly ring
ionomers. This would lead to a better chemical classi closure. These effects are known to occur in the aging
fication of the variety of absorptions that are nowadays of oil [6, 15], but do not occur in ionomers. Ring clos
summarized as metal ure and the resulting strain on the molecular structure
carboxylates.
are indeed known to increase the of the
frequency
maximum of CH moieties same
CH stretch vibration absorption [41]. The is
true for CH moieties close to an oxygen atom [29]. The
The intensity of the CH stretch vibrations is commonly origin of these effects ismainly located in the network
seen as a measure of the oil content in a fraction of the aged oil. A better understanding of these
quantitative
The intensities of these are shifts may therefore become a valuable tool in the
sample. decreasing peaks
as a decrease in aliphatic moie further characterization of the polymeric fraction.
interpreted accordingly
ties due to the loss of volatile However, the
products.
amount of volatile in the literature
products reported
seems to be et al. mention a
extremely high. Meilunas
60% intensity decrease of the CH stretch vibration [10].
Rasti and Scott even report a 92% decrease of the
=
absorption intensity at 2930 cm"1 (log A()/A1 1.1) for a
seems
vermilion-pigmented paint film [13]. It unlikely
that the loss of volatile aliphatic materials during aging is
so extensive that it suffices to this effect.
explain
However, a better has not yet been
explanation given.
It has been noted et al. that the
by Mallegol decreasing
is combined with a shift of the
intensity absorption
to shorter
maxima wavelengths [5]. A shift of the CH
vibrations has also been observed in the spectra reported
here. The maximum absorption of ultramarine
was found to be as
as 2945 and 0.4 0.6
pigmented paint high
2873 cm-1, while the in the oil Height
absorptions original
medium are at 2927 and 2855 cm-1. the
binding Despite Figure 22 Comparison of the height and area of theCH stretch
relatively large shifts, the actual widths of the peaks vibrationband at 2950-2920 cm-1 inall spectra presented inFigures
remained constant, as the area of the 5-21. See experimental section forparameters.
remarkably

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 20 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

CONCLUSIONS research at AMOLF forms part of FOM research

programmes 28 and 49.

Several infrared spectra of traditionally prepared and

naturally paints have been presented to

aged investigate REFERENCES
the long-term influence of the pigments on the oil
medium. Reaction of metal ions from 1 Gombrich, E.H., The Story ofArt, Phaidon Press, London
products
pigments and the oil
binding medium were found as (1995).
2 Dunkerton, J., Giotto toD?rer, National Gallery Publications,
metal carboxylates for a number of pigments. Other
London (1991).
indications for reactions influenced were
by pigments 3 Muizebelt, W.J., Donkerbroek, J.J.,Nielen, M.W.F., Hussem,
found in the aliphatic CH at ~2930 cm"1
absorption and Zabel, K.H.,
J.B., Biemond, M.E.F., Klaasen, R.P.,
and the carbonyl at ~1740 cm"1. The
absorption 'Oxidative crosslinking of unsaturated fatty acids studied with
hypsochromic shift of the CH vibration is assigned to mass spectrometry', Journal ofMass Spectrometry31(5) (1996)
oxidation and ring closure reactions in the network part 545-554.
of the oil. These shifts are especially pronounced in 4 Muizebelt, W.J., Nielen, M.W.F., Klaasen, R.P., and Zabel,

paints pigmented by ochres, Naples yellow and K.H., 'Crosslink mechanisms of high-solids alkyd resins in the
ultramarine. presence of reactive diluents', Progress in Organic Coatings 40
can be (2000) 121-130.
The intensity of the ester peak at 1740 cm"1
5 Mallegol, J., Gardette, J.L., and Lemaire, J., 'Long-term
greatly reduced by the presence of particular pigments,
behavior of oil-based
varnishes and paints I. Spectroscopic
indicatinghydrolysisof the triglyc?rides.
This decreased
analysis of curing drying oils', Journal of theAmerican Oil
intensity is especially clear for the zinc white and red
Chemists Society 76 (1999) 967-976.
lead paints, where the absorbance of the ester band is
6 Wexler, H., 'Polymerization of drying oils', Chemical Reviews
lower than the absorbance of the CH vibrations.
64(6) (1964) 591-611.
this relationship cannot be made 7 Porter, N.A., Lehman, L.S., Weber,
Unfortunately, fully B.A., and Smith, K.J.,
as the of the CH vibrations is not 'Unified mechanism for polyunsaturated fatty acid autoxida
quantitative, intensity
a valid unit for the amount of oil material. tion. Competition of peroxy radical hydrogen atom abstrac
and shifts of the carbonyl have tion, b-scission, and cyclization', Journal of theAmerican
Broadening absorption
been observed in most of the aged paints. These effects Chemical Society 103 (1981) 6447-6455.
8 Porter, N.A., 'Mechanisms for the autoxidation of polyunsat
are to the formation of new,
assigned remarkably
urated lipids', Accounts of Chemical Research 19 (1986) 262
at 1707 ? 2 and 1780 ? 5 cm"1.
reproducible absorptions 268.
The number of carboxylic acids, to which at
absorption 9 Swern, D., Scanlan, J.T., and Knight, H.G., 'Mechanism of
1707 cm"1 is assigned, reduces upon the formation of
the reactions of oxygen with fattymaterials. Advances from
metal carboxylates. This effect was observed for lead 1941 through 1946', Journal of theAmerican Oil Chemists' Society
zinc white, red lead and Naples The
white, yellow. (1948) 193-200.
is very useful in the
characteristic carbonyl pattern 10 Meilunas, R.J., Bentsen, J.G., and Steinberg, A., 'Analysis of
investigation of oil paint, as it is normally not disturbed aged paint binders by FTIR spectroscopy', Studies inConserva
tion35 (1990) 33-51.
by any pigment absorptions.
11 Luxan, M.P., and Dorrego, F., 'Reactivity of earth and
synthetic pigments with linseed oil', Jocca-Surface Coatings
ACKNOWLEDGEMENTS International82 (1999) 390.
12 Lazzari, M., and Chiantore, O., 'Drying and oxidative
The samples described in this studywere provided by degradation of linseed oil', PolymerDegradation and Stability 65
Wim Muizebelt, Martin and Jorrit van den Berg.
Paans (1999) 303-313.
were made available for 13 Rasti, F., and Scott, G., 'The effects of some common
The naturally aged paint samples
research by Dr Andreas Burmester and Dr Johann Koller pigments on the photo-oxidation of linseed oil-based paint
media', Studies inConservation 25 (1980) 145?156.
(Doerner Institut, Munich), Ms Kate Helwig and Dr Ian
14 Hess, M., Hamburg, H.R., and Morgans, W.M., Hess's Paint
Wainwright (Canadian Conservation Institute, Ottawa),
Film Defects, Chapman and Hall, London (1979).
and Mr Hans-Christoph von Imhoff (private restorer, 15 Sebedio, J.L., and Grandgirard, A., 'Cyclic fatty acids: natural
These FTIR studies are part of the
Switzerland). priority sources, formation during heat treatment, synthesis and bio
MOLART of Ageing in
programme (Molecular Aspects logical properties', Progress inLipid Research 28 (1989) 303?336.
Painted Art), which is funded by the Dutch Organisa 16 Chan, H.W.S., and Coxon, D.T., in
'Lipid peroxides',
tion forScientificResearch (NWO) and theFoundation Autoxidation ofUnsaturated Lipids, ed. H.W.S. Chan, Academic
for Fundamental Research on Matter The Press, London (1987) 17-50.
(FOM).

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 FTIRSTUDIES OF THE EFFECTS OF PIGMENTSON THE AGINGOF OIL 21

-
17 Grosch, W., 'Reactions of hydroperoxides products of low History and Characteristics,Volume 1, ed. R.L. Feller, Cambridge
molecular weight', in Autoxidation of Unsaturated Lipids, ed. University Press and National Gallery of Art,Washington DC
H.W.S. Chan, Academic Press, London (1987) 95-139. (1986) 219-254.
18 Figge, K., 'Dimeric fatty acid[l-14C] methyl esters. I. 34 Grissom, CA., 'Green earth', inArtists' Pigments,A Handbook of
Mechanisms and products of thermal and oxidative-thermal History and Characteristics,Volume ?, ed. R.L. Feller, Cam
their
-
reactions of unsaturated fatty acid esters literature review', bridge University Press and National Gallery of Art,

Chemistry and Physics ofLipids 6 (1971) 164-182. Washington DC (1986) 141-167.

19 Mills, J., and White, R., 'Analyses of paint media', National 35 Languri, G.M., Molecular studies ofAsphalt, Mummy and Kassel

Gallery Technical Bulletin 4 (1980) 65-68. Earth Pigments: Their Characterisation, Identificationand Effect on
20 Derrick, M.R., 'Infraredmicrospectroscopy in the analysis of theDrying of Traditional Oil Paint (Molart Report 9), PhD
cultural artifacts', in PracticalGuide toInfrared
Microspectroscopy,ed. thesis,University of Amsterdam (2004).
H.J. Humecki, Marcel Dekker, New York (1995) 287-322. 36 Feller, R.L., and Johnston-Feller, R.M., 'Vandyke brown', in
21 Van den Berg, J.D.J., Van den Berg, K.J., and Boon, J.J., Artists' Pigments: A Handbook of their History and Characteristics,
'Determination of the degree of hydrolysis of oil paint samples Volume 3, ed. E.W. FitzHugh, Oxford University Press and
using a two-step derivatisation method and on-column Gallery of Art, Washington DC
National (1997) 157-190.
GC/MS', Progress inOrganic Coatings 41 (2001) 143-155. 37 K?hn, H., 'Zinc white', inArtists' Pigments,A Handbook of their
22 Osawa, Z., 'Role of metals and metal-deactivators in polymer History and Characteristics,Volume 1, ed. R.L. Feller, Cambridge
degradation', PolymerDegradation and Stability20 (1988) 203-236. University Press and National Gallery of Art,Washington DC
23 Boon, J.J.,Peulv?, S.L., van den Brink, O.F., Duursma, M.C., (1986) 169-186.
and Rainford, D., 'Molecular aspects of mobile and stationary 38 K?hn, H., 'Bleiweiss und seine Verwendung in der Malerei

phases in ageing tempera and oil paint films', in Early Italian II', Farbe und Lack 73 (1967) 209-213.
Paintings Techniques and Analysis, Limburg Conservation 39 Carlyle, L., The Artist's Assistant, Oil Painting Instruction
Manuals
Institute,Maastricht (1997). and Handbooks in Britain 1800-1900 with Reference to Selected
24 Gettens, R.J., K?hn, H., and Chase, W.T., 'Lead white', in Eighteenth-Century Sources, Archetype Publications, London
Artists' Pigments: A Handbook of their
History and Characteristics, (2001).
Volume 2, ed. A. Roy, Oxford University Press, Washington 40 Hartshorn, J.H., 'Time-lapse infrared spectroscopic investiga
DC (1993) 67-82. tion of alkyd and linseed oil cure', Journal ofCoatings Technology
25 Susi, H., and Byler, D.M., 'Protein structureby Fourier transform 54 (1982) 53-61.
infrared spectroscopy: second derivative spectra', Biochemical 41 Colthup, N.B., Daly, L.H., andWiberley, S.E., Introduction to
and Biophysical Research Communications 115 (1983) 391-397. Infraredand Raman Spectroscopy, 1st edn, Academic Press, New
26 Arrondo, J.L.R., Muga, A., Castresana, J., and Goni, F.M., York (1964).
'Quantitative studies of the structure of proteins in solution by 42 Matura, R., 'Divalent metal salts of long chain fatty acids',
Fourier-transform infrared-spectroscopy', Progress in Biophysics Journal of theChemical Society ofJapan 86 (1965) 560-572.
andMolecular Biology 59 (1993) 23-56. 43 Ishioka, T., 'Infrared spectral change in a zinc salt of an
27 Mossoba, M.M., McDonald, R.E., Roach, J.A.G., Fingerhut, ethylene-methacrylic acid ionomer on water-absorption',
D.D., Yurawecz, M.P., and Sehat, N., 'Spectral confirmation of PolymerJournal 25 (1993) 1147-1152.
trans monounsaturated C-18 fatty acid positional isomers', 44 Zeng, Z.H., Wang, S.H., and Yang, S.H., 'Synthesis and
Journal of theAmerican Oil Chemists Society 74 (1997) 125-130. characterization of PbS nanocrystallites in random copolymer
28 O'Neil, L.A., 'Application of infrared spectroscopy to the ionomers', Chemistry ofMaterials 11 (1999) 3365-3369.
study of the drying and yellowing of oil films', Paint Technology 45 Ishioka, T., Shimizu, M., Watanabe, I., Kawauchi, S., and
27(1) (1963) 44-47. Harada, M., 'Infrared and XAFS study on internal structural
29 Smith, B., InfraredSpectral Interpretation,
A SystematicApproach, change of ion aggregate in a zinc salt of poly(ethylene-co
CRC Press, London (1999). methacrylic acid) ionomer on water absorption', Macromolecules
30 Ma, K., van de Voort, F.R., Sedman, J., and Ismail, A.A., 33 (2000) 2722-2727.
'Stoichiometric determination of hydroperoxides in fats and 46 Hashimoto, H., Kutsumizu, S., Tsunashima, K., and Yano, S.,
oils by Fourier transform infrared spectroscopy', Journal of the 'X-ray absorption spectroscopic studies on pressure-induced
American Oil Chemists Society 74 (1997) 897-906. coordination-structural change of a zinc-neutralized ethylene
31 Ma, K., van de Voort, F.R., Ismail,A.A., and Sedman, J., 'Quan
methacrylic acid ionomer', Macromolecules 34 (2001) 1515-1517.
titative determination of hydroperoxides by Fourier transform 47 Kutsumizu, S., Instrumental Analysis Center, Gifu
University,
infrared spectroscopy with a disposable infrared card', Journal Japan, personal communication (2002).
of theAmerican Oil Chemists Society 75 (1998) 1095-1101.
32 Frilette, V.J., 'Drying oil and oleoresinous varnish films,
increase in acidity on ageing', Industrial and
Engineering AUTHORS
Chemistry 38 (1946) 493-496.
33 Wainwright, I.N.M., Taylor, J.M., and Harley, R.D., 'Lead Jaap van der Weerd graduated in molecular sciences
antimonate yellow', in Artists' Pigments, A Handbook of their from Wageningen
Agricultural University in 1998. He

STUDIES IN CONSERVATION 50 (2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions
 22 J. VAN DER WEERD, A. VAN LOON AND J.J. BOON

joined the MOLART project to perform infrared huis in The Hague. Address: FOM Institute for Atomic and
reflection studies and various microspectroscopic studies Molecular Physics,Kruislaan 407, 1098 SJAmsterdam,The
(imagingVIS and FTIR) of paint materials and paint Netherlands. Email: a.v.loon@amolf.nl
cross-sections. Part of this work was submitted as a PhD
in geology at the
thesis titled 'Microspectroscopic analysis of traditional oil Jaap J. Boon trained and chemistry
to the University of Amsterdam in 2002. Since Universities of Amsterdam and Utrecht, and at Delft
paint'
2003 he has been working as research associate at Technical After studies in
Imperial University. postdoctoral
College London. Address: Department of Chemical Engin marine experimental and microbiology, he
biology
eering and Chemical Technology, Imperial College, London started in 1983 as research associate in the FOM Institute
SW7 2AZ, UK. for Atomic and Molecular Physics. He became professor
of molecular at the University of
palaeobotany
Annelies van Loon received aMSc in inorganic chem Amsterdam in 1988. He masterminded and coordinated

istry from the University of Amsterdam in 1994 and the NWO Priority Project MOLART (Molecular
a in paintings conservation from of Ageing in Art), granted in 1995. Presently,
postgraduate degree Aspects
the Limburg Conservation Institute (SRAL, Maastricht) he is head of the Molecular Paint Research group at

in 2000. She is currently working in the Molecular AMOLF and Professor of Analytical Mass Spectrometry
at the University as van Loon.
Painting Research group at the FOM Institute AMOLF. of Amsterdam. Address: for
In addition, she is part-time conservator at the Maurits Email: boon@amolf.nl

?
R?sum? ?tude d?crit comment le spectre infrarouge d} une peinture change enfonction de son vieillissement. U attention
Cette
sur sur les
est
port?e Vinfluence du pigment changements ? long terme dans le liant ? Vhuile. Plusieurs peintures vieillies
naturellement contenant des pigments diff?rents ont ?t? analys?es par spectroscopie infrarouge ? transform?e de Fourier. Un des
est le et V?largissement de la bande carbonyle dus ? la
effets les plus marqu?s observ?s dans le spectre infrarouge d?placement
autre sur le liant ? Vhuile est la catalyse de Vhydrolyse des triglyc?rides,
formation d'acides carboxyliques. Un effet des pigments
caract?ris?e par la diminution de Vintensit? de Vabsorption des esters. Finalement, la nature des pigments a un effetprononc? sur
V absorption des groupements CH. Il est clair, au vu de ces r?sultats, que les pigments peuvent alt?rer defa?on significative le

spectre infrarouge des liants ? Vhuile,

et devraient donc ?tre identifi?s pr?alablement afin d'?valuer correctement les spectres
des peintures ? Vhuile.
infrarouges

? von Bindemitteln bei der Alterung mittels Infrarotspektroskopie

In dieser Studie wird die Ver?nderungen
Zusammenfassung
untersucht. Besonderes Augenmerk ist dabei auf den Einfluss der Pigmente auf die Alterung von ?lmalschichten gerichtet.
Verschiedene nat?rlich gealterte Malschichten mit verschiedenen Pigmenten wurden mit Hilfe der Fouriertransforminfrarotspektro
untersucht. Entsprechend der Bildung von Carboxylgruppen ist die Hauptver?nderung bei den Spektren eine
skopie (FTIR)
Ein anderer, durch die Katalyse derHydrolyse der Triglyc?ride durch die Pigmente verursachter
Verbreiterung der Carbonylbanden.
ist eine Verringerung der Intensit?t der Esterabsorbtion. Dar?ber hinaus hat das Pigment starken Einfluss auf die
Effekt,
Absorbtion der CH-Streckschwingung. Gem?? diesen Ergebnissen wird es klar, dass Pigmente erheblichen Einfluss auf die

sollten, bevor das Bindemittel mit Infrarotspektro

Infrarotspektren
von trocknenden ?len haben und daher identifiziert werden
untersucht wird.
skopie

? en el espectro infrarrojo de ciertas pinturas como resultado del envejecimiento.

Resumen Esta investigaci?n describe los cambios
Se centra en la influencia del pigmento en los cambios a largo plazo que pueden producirse en un aglutinante oleoso. Una serie de
muestras de pinturas envejecidas de manera natural y preparadas con se analizaron por medio de espectro
diferentes pigmentos
de Fourier (FTIR). Uno de los efectos m?s pronunciados observados en los espectros de las
scopia infrarroja transformada pel?culas
de pintura envejecidas es el salto y ensanchado de la banda correspondiente a los grupos carbonilos debido a laformaci?n de ?cidos
carbox?icos. Otro efecto producido por los pigmentos en el aglutinante oleoso es la cat?lisis de la hidr?lisis de los triglic?ridos, esto
de intensidad en la absorci?n de esteres. Finalmente, la naturaleza de los pigmentos incluidos en
puede deducirse por el descenso
este estudio tiene un en la extensi?n de las absorciones por grupos CH. Estos resultados indican claramente que
profundo efecto
los pigmentos pueden alterar los espectros infrarrojos de los aceites secativos, y deber?an, por tanto, ser identificados de antemano
en con aceites secativos.
para asegurar la correcta interpretaci?n de los espectros infrarrojos pinturas aglutinadas

STUDIES IN CONSERVATION 50(2005) PAGES 3-22

This content downloaded from 131.170.6.51 on Wed, 03 Feb 2016 12:12:08 UTC
All use subject to JSTOR Terms and Conditions