Anal Bioanal Chem (2012) 402:1567–1584
DOI 10.1007/s00216-011-5369-5
ORIGINAL PAPER
UV ageing studies: evaluation of lightfastness declarations
of commercial acrylic paints
Valentina Pintus & Shuya Wei & Manfred Schreiner
Received: 19 May 2011 / Revised: 18 August 2011 / Accepted: 24 August 2011 / Published online: 16 September 2011
# Springer-Verlag 2011
Abstract The lightfastness declarations of several different
commercial acrylic paints and different quality series were
tested by artificial UV ageing. To evaluate their lightfastness
declarations, three acrylic colours (cadmium red, ultrama-
rine blue and chromium oxide green) from six companies
(Lascaux, Liquitex, Lukas, Rembrandt, Schmincke, and
Winsor & Newton) were analysed before and after UV
exposure. Characterisation and identification of these
materials were carried out with Py–GC/MS, FTIR–ATR
analyses, and colour measurements. Particular attention was
focused on the Py–GC/MS measurements and on compar-
ison of the single-shot method for pyrolysis of polymers
and the double-shot mode which enables a unique
combination of pyrolysis methods for analysis of polymers
and thermal desorption for documentation of the volatile
compounds. Depending on the particular company and the
specific value of the lightfastness declaration, different
binding media (i.e. poly(EA/MMA), poly(nBA/MMA), and
poly(2-EHA/MMA)), and fillers (i.e. kaolinite, calcium
carbonate, barite, and talc) were characterised and identified
by Py–GC/MS and FTIR–ATR analyses. After UV expo-
sure, several alteration processes with consequent formation
Published in the special issue Analytical Techniques in Art,
Archaeology and Conservation Science with guest editor Oliver Hahn.
V. Pintus : S. Wei : M. Schreiner
Institute of Science and Technology in Art, Academy of Fine Arts,
Schillerplatz 3,
1010 Vienna, Austria
V. Pintus (*) : M. Schreiner
Institute of Chemical Technology and Analytics,
Analytical Chemistry Division, Vienna University of Technology,
Getreidemarkt 9/161,
1060 Vienna, Austria
e-mail: v.pintus@akbild.ac.at
of volatile compounds or new products were observed by
both techniques, especially for the blue paints. In
particular, the double-shot mode of Py–GC/MS enabled
the detection of oxidation products, which could not be
detected with the single-shot mode. Comparison of the
lightfastness declarations for each of the blue, green, and
red paints and the noted alterations broadly agreed for
most of the paints.
Keywords Py–GC/MS . FTIR–ATR . Double-shot
technique . Acrylic modern paints . Lightfastness index . UV
ageing
Introduction
Artist acrylic paints in the form of waterborne emulsions
started to have a significant impact on the paint market after
the Second World War [1]. Because of their fast drying and
environmentally friendly properties, and because of the
presence of water instead of organic solvents, emulsion
acrylic materials have been revolutionary in the paint and
coating sector.
Acrylic emulsions are generally called “latex” (disper-
sion of acrylic polymers in water) and are characterised by
four basic components: water, monomer, initiator, and
surfactant. Several detailed studies of their composition
have been reported in the literature [1–11]. Three different
types of acrylic co-emulsion are commonly used for paint
formulations: poly(ethyl acrylate/methyl methacrylate (EA/
MMA), poly(butyl acrylate/methyl methacrylate) (nBA/
MMA), and 2-ethylhexyl acrylate/methyl methacrylate (2-
EHA/MMA). In the early years, p(EA/MMA) was com-
monly used, but since the late 1980s paints with a p(nBA/
MMA) binder, which increases toughness and hydropho-
1568
bicity, have been adopted and used by many companies
producing artists’ acrylic emulsion paints [12]. In recent
years, 2-ethylhexyl acrylate/methyl methacrylate (2-EHA/
MMA) has also been widely used.
Surfactants, which are essential additives for reduction of
the interfacial tension between the monomers and water, are
important components of acrylic emulsions. These additives
can be anionic (e.g. sodium lauryl sulfate or dodecylbenzene
sulfonate), cationic (usually based on quaternary ammonium
compounds), or non-ionic (e.g. alkyl phenol ethoxylates).
Non-ionic surfactants, especially those based on polyethox-
ylates, have been studied [13–16] in recent years, because of
their extensive use and their exudation to the surface of the
acrylic emulsion paint films causing changes in gloss and
surface roughness [13].
The composition of paint formulations are particularly
complex. They are mainly a mixture of an acrylic emulsion, a
pigment, and an extender (or filler), with other additives. The
addition of extenders is not only principally related to reducing
the cost and increasing the volume of the material—extenders
can also have beneficial effects on the paint.
Different types of inorganic extender, for example talc
(Mg3(Si4O10)(OH)2), barite (BaSO4), calcite (CaCO3),
kaolinite (Al2Si2H4O9), and various forms of silica are
commonly used. The demand for various types of extender
for use in paints is increasing, because of their ability to
modify the quality of paints, depending on their grain size,
refractive index, brightness, and chemical composition [17].
These four components outlined above are necessary for
artists’ acrylic paints.
During the last 60 years several companies have been
developing a large variety of acrylic paint colours. In 1955,
Permanent Pigment (Liquitex, New Jersey, USA) was the first
manufacturer to commercially produce water-based acrylic
paints [18]. Since the Second World War high-quality artists’
acrylic paints have been introduced by Schmincke (Ger-
many) [19]. These modern artists’ paints—under the brand
name PRIMAcryl—became an important addition to the
range, especially in the German home-market. Several other
companies, including Lascaux (Switzerland) since 1963 [20]
and Lukas (Germany) since 1964 [21], have also been
commercially producing artist acrylic colours, mostly based
on waterborne emulsions. In 1970 Winsor & Newton (UK)
introduced their first assortment of artists’ acrylic paints [22].
These are only a few examples, which were selected for this
study, from a long list of manufacturers that produce acrylic
paint materials, and who, over time, have constantly
improved and/or modified the chemical compositions of the
formulations to better satisfy artists’ requirements.
Acrylic artist paints have been widely used in paintings
and also for artwork exposed to outdoor conditions, where
ultra violet (UV) light has an important effect on their
photo-oxidative stability, especially the part of its wave-
V. Pintus et al.
lengths that normally cannot pass through normal window
glass, for example UV-B (315 to 280 nm wavelength, λ),
which can cause discolouration, cracks, and other damage
to acrylic materials. Over the past 20 years, the effects on
acrylic emulsions of photo-oxidation reactions due to UV
light have been studied in detail [23–26], using different
sources of artificial UV light, for example fluorescent [23,
24, 26] or mercury high-pressure lamps [25]. Investigations
with fluorescent lamps and UV filters to remove the
radiation at wavelengths below 400 nm generally show
acrylic emulsions to be highly stable to photo-oxidation
[26]. Chiantore et al. [27] used a xenon light source filtered
for λ< 295 nm for investigation of acrylic polymers
characterised by long ester groups, for example n-butyl
groups, and detected rapid and extensive cross-linking in
combination with some fragmentation, because of the
favoured oxidation of the tertiary carbon of the butyl
group. When the alkyl side groups are short, chain scission
prevails over cross linking reactions [28]. In contrast with
these studies, the effect of UV-B light on the stability and/or
degradation of materials in artworks under outdoor con-
ditions has not been widely studied.
Pigmented acrylic emulsions have also been investigated,
both before and after UV exposure. Doménech-Carbó et al.
[29] studied the behaviour of artists’ acrylic and poly(vinyl
acetate) paint films in simulated daylight ageing and
observed notable changes in the paints, depending on the
type of pigment and binding media. Pintus et al. [3] were
among the first to use double-shot pyrolysis GC/MS,
complemented by FTIR–ATR analyses, in UV ageing studies.
Both methods were used to investigate two different acrylic
binding media—pure and mixed with different inorganic
pigments—before and after UV exposure. The results
revealed more pronounced alterations for acrylic binding
media mixed with pigments than for pure acrylics
However, more studies of the effect of inorganic pigments
and fillers on acrylic emulsions in paint formulations are
necessary [3].
Nowadays the labelling on paint tubes provides many
details for artists about the properties of the paint, including
a colour index, pigment names, a series number, opacity
and glazing, and a lightfastness index. However, some
important details, for example chemical composition are
kept secret. The lightfastness index is usually established by
following standards of the American Society for Testing
and Materials (ASTM), a widely recognized international
organization for standardization with more than thirty
thousand members in 135 countries. Twelve thousand
ASTM standards are used around the world by industry
and governments. Fifteen of these were developed by
ASTM D01.57, where D01 specifies the Committee that
oversees paints and the number 57 stands for the subcom-
mittee “Artists’ Materials”.
Evaluation of lightfastness declarations of acrylic paints
Two ASTM standards which relate to the lightfastness
index of synthetic artists’ paints, have been developed:
D5383 (“Standard Practice for Visual Determination of the
Lightfastness of Art Materials by Art Technologists”) [30]
and D5398 (“Standard Practice for Visual Evaluation of the
Lightfastness of Art Materials by the User”) [31]. The first
is based on a method for testing the lightfastness of art
materials by use of blue wool fading cards. This standard
does not require sophisticated analytical instruments to
measure the result. Standard D5398 is a simplified version
of standard D5383, with the advantage that individual
artists can evaluate their own materials for lightfastness.
Usually, the lightfastness of art materials is evaluated on the
basis of the methods outlined by these two standards.
According to the results of the lightfastness evaluations, paint
materials are classified by different lightfastness qualities.
This seems ideal, but the different paint companies use
different ways to express the lightfastness of their products.
For instance, Winsor & Newton and Liquitex use I (excellent),
II (very good), and III (good) whereas Lukas, Lascaux, and
Schmincke apply ***** (extremely lightfast), **** (good
lightfastness), *** (lightfast), ** (limited lightfast), * (less
lightfast), and Rembrandt uses +++ (excellent) and ++ (very
good).
The objective of the work discussed in this paper was
analytical evaluation of the lightfastness classifications of
three commercial acrylic colours (cadmium red, ultramarine
blue, and chromium oxide green) from six different
companies, keeping in mind the UV sensitivity of paints,
especially those used for artwork under outdoor conditions
(e.g. mural paintings). For this purpose, characterisation
and identification of the main compounds in the selected
acrylic paint formulations have been performed by pyrol-
ysis gas chromatography mass spectrometry (Py–GC/MS)
in the single-shot and double-shot modes, by Fourier
transform infrared spectroscopy–attenuated total reflectance
(FTIR–ATR), and by colour measurement. In comparison
with previous work [3], the double-shot technique and
FTIR–ATR analyses in this study were applied to commer-
cial paints. We also investigated colour alterations of these
materials from UV exposure by using colour measurements;
this was not carried out in the previous work [3].
FTIR–ATR and colour measurement analyses are non-
invasive methods whereas Py–GC/MS investigations are
invasive and destructive. Investigation of the chemical
composition of both the binding media and pigments is
fundamental for understanding their physical properties and
the lightfastness of the paints. Unfortunately, it was not
possible to find the same colour with different lightfastness
index classification produced by a single company. After
chemical characterisation of the selected paints, they were
exposed to UV radiation to investigate UV-induced chem-
ical alterations. The objective of the work was to gain better
1569
understanding of the UV resistance of different paint
formulations and colours and the variable classifications
used by the different companies for their lightfastness
declarations. So far, there have been no independent,
reproducible scientific evaluations of the lightfastness of
commercial acrylic paints. Therefore, the results presented
in this paper are of potential interest for anyone involved in
the use of paints, including chemists, artists, curators,
conservators, the paint industry, etc.
Experimental
Sample preparation
Three acrylic paint colours—ultramarine blue, cadmium
red, and chromium oxide green—from six companies—
Lascaux, Liquitex, Lukas, Rembrandt, Schmincke, and
Winsor & Newton—all labelled with a lightfastness index
by their respective producers (Table 1) were investigated.
Approximately 200 mg of each sample were cast on glass
plates, producing dried films with an average thickness of
0.13 mm. Three identical samples of each acrylic paint
colour were prepared, to obtain sufficient sample for the
tests in the UV chamber. After drying for 3 months at room
temperature, all of the glass plates were placed in the UV
chamber, except for the reference samples for the investi-
gation of the unaged compositions.
UV ageing
UV ageing of the samples was carried out in a UV chamber,
UVACUBE SOL 2/400 F, produced by Dr Hönle UV-
Technology, Germany. The UV light source was a 910 W
m−2 xenon arc solar simulator, with an incorporated H2 filter,
which provides radiation with wavelengths between 295 nm
and 800 nm. The chamber temperature was 48.8 °C. No
control of the relative humidity (RH) was possible in the UV
chamber used, therefore the RH varied between 30 and 35%
depending on the RH in the ambient atmosphere. Samples
were aged for 31 and 83 days, respectively.
Pyrolysis gas chromatography–mass spectrometry
(Py–GC/MS)
Py–GC/MS analysis was performed for identification and
characterisation of the samples before and after UV exposure.
Between 80 and 300 μg of the samples were scraped from the
glass plates with a scalpel and put in a sample cup (ECO-CUP
Frontier Lab, Japan) for analysis. In this investigation, Py–
GC/MS analyses were performed with a PY AOC-20i
(Frontier Lab, Japan) pyrolyser unit combined with a
GCMS-QP2010 Plus (Shimadzu, Japan) equipped with a
1570 V. Pintus et al.

Table 1 List of the commercial acrylic paints investigated and their technical properties as declared by the companies. The chemical compositions
of binding media and extenders were determined in this study

Sample Colour Pigment Chemical composition Colour index: Lightfastnessa Series

classical name generic name

Lascaux—Artist, Switzerland Blue Ultramarine p(2-EHA/MMA)+Na8Al6Si6O24.Sx+Kaolinite PB 29 *** 2

blue (Al2Si2H4O9)
Lascaux—Artist, Switzerland Green Chromium p(nBA/MMA)+Cr2O3 +Calcite (CaCO3) PG 17 ** 2
oxide green
Lascaux—Artist, Switzerland Red Cadmium red p(2-EHA/MMA)+CdS, xCdSe+Calcite PR 108 *** 4
medium (CaCO3)
Liquitex—Professional Blue Ultramarine p(nBA/MMA)+Na8Al6Si6O24.Sx+Kaolinite PB 29 I 1A
Acrylic Artist Color, USA/ blue (Al2Si2H4O9)
Canada
Liquitex—Professional Acrylic Green Chromium p(nBA/MMA)+Cr2O3 PG 17 I 2
Artist Color, USA/Canada oxide green
Liquitex—Professional Acrylic Red Cadmium red p(nBA/MMA)+CdS, xCdSe PR 108 I 5
Artist Color, USA/Canada light
Lukas Cryl—Pastos, Blue Ultramarine p(EA/MMA)+Na8Al6Si6O24.Sx+Kaolinite PB 29 *** 1
Germany blue light (Al2Si2H4O9)+Barites (BaSO4)+Calcite
(CaCO3)
Lukas Cryl—Pastos, Green Chromium p(EA/MMA)+Cr2O3 +Kaolinite (Al2Si2H4O9)+ PG 17, PG 7, *** 2
Germany oxide green Barites (BaSO4) PY 3, PY
light 42
Lukas Cryl—Pastos, Red Cadmium red p(EA/MMA)+CdS, xCdSe+Kaolinite PR 108, P0 *** 3
Germany light (Al2Si2H4O9)+Barites (BaSO4) 20
Rembrandt—Artists Quality Blue Ultramarine p(nBA/MMA)+Na8Al6Si6O24.Sx+Kaolinite PB 29 +++ 1
Extra Fine, Holland blue (Al2Si2H4O9)
Rembrandt—Artists Quality Green Chromium p(nBA/MMA)+Cr2O3 +Calcite (CaCO3) PG 17 +++ 2
Extra Fine, Holland oxide green
Rembrandt—Artists Quality Red Cadmium red p(nBA/MMA)+CdS, xCdSe+Calcite (CaCO3) PR 108 +++ 3
Extra Fine, Holland light
Schmincke—PRIMAcryl, Blue Ultramarine p(2-EHA/MMA)+Na8Al6Si6O24.Sx+Kaolinite PB 29 **** 1
Germany blue (Al2Si2H4O9)
Schmincke—PRIMAcryl, Green Chromium p(2-EHA/MMA)+Cr2O3 +Barites (BaSO4) PG 18 ***** 1
Germany oxide green
Schmincke—PRIMAcryl, Red Cadmium red p(2-EHA/MMA)+CdS, xCdSe+Talc PO 20 ***** 2
Germany light (Mg3(Si4O10)(OH)2)
Winsor & Newton—Artists’ Blue Ultramarine p(2-EHA/MMA)+Na8Al6Si6O24.Sx PB 29 I 2
Acrylic, England blue
Winsor & Newton—Artists’ Green Chromium p(2-EHA/MMA)+Cr2O3 PG 17 I 3
Acrylic, England oxide green
Winsor & Newton—Artists’ Red Cadmium red p(2-EHA/MMA)+CdS, xCdSe+Barites PR 108 I 3
Acrylic, England medium (BaSO4)
a
*I, excellent; II, very good; III, good; *****, extremely lightfast; ****, good lightfastness; ***, lightfast; **, limited lightfast; *, less lightfast; +
++, excellent; ++, very good

capillary column Ultra Alloy-5 (5% diphenyl 95% dimethyl-
polysiloxane) with 0.25 mm internal diameter, 0.25 μm film
thickness, and 30 m length (Frontier Laboratories, Japan).
NIST 05 and NIST 05 s Library of Mass Spectra were used for
identifying the compounds.
Particular attention was paid to comparison of two
different analytical methods:
1. the single-shot method and pyrolysis of the polymer for
analysis; and
2. the double-shot method, which enables combination of
the thermal desorption of volatile compounds with
pyrolysis of the polymers.
To achieve thermal desorption of volatile compounds,
the sample, in a small cup, is dropped by the autosampler
into the furnace of the pyrolyser and heated with a
temperature ramp (e.g. from 100 to 250 °C in 12 min and
50 s). When the thermal desorption program is complete,
the sample-cup containing the remaining fraction is pulled
up from the heated zone while the volatile organic
compounds produced by thermal desorption are analysed
by GC/MS. Meanwhile the furnace is cooled to approxi-
mately 60 °C (auto-cooling) then heated to the pyrolysis
temperature (e.g. 600 °C). As soon as GC/MS separation
and detection of the volatile compounds is complete, the
sample cup is dropped for a second time into the pyrolyser
Evaluation of lightfastness declarations of acrylic paints
furnace to perform flash pyrolysis, and the pyrolysis
products are analysed by GC/MS [3].
The GC column temperature conditions were: initial
temperature 40 °C, held for 5 min, followed by a
temperature ramp of 10°min−1 to 292 °C. The helium gas
flow was set at 1 mL min−1 and mass spectra were recorded
under electron impact ionization at 70 eV. For the single-
shot analyses the pyrolysis temperature was set at 600 °C
and held for 1 min, and the temperature of the pyrolysis
interface and injector was set at 250 °C.
The double-shot conditions were: for thermal desorption
the temperature was set at 100 °C, held for 2 min, and then
increased by 20°min−1 to 250 °C and held there for 2 min.
Fourier transform infrared spectroscopy–attenuated total
reflectance (FTIR–ATR)
FTIR–ATR analyses were performed with an Alpha FT-IR
Platinum ATR instrument (Bruker Optics, Germany) equipped
with a deuterated triglycine sulfate detector (DTGS) and with a
diamond crystal. Spectra were acquired in the spectral range
between 4000 and 370 cm−1 performing 64 scans at 4 cm−1
resolution. The resulting spectra were collected and evaluated
with the spectrum software Opus from Bruker Optics.
Colour measurements
A SPM50 (Gretag–Macbeth, Switzerland) instrument was
used to obtain spectra in the visible range. Reflectance
measurements were carried out using a D65 lamp in the
range of 380–730 nm. Reflection was measured relative to
the white standard of the instrument and a 10° Standard
Observer was used. For the UV ageing studies, the total
colour values (ΔE*) were obtained according to the
Commission Internationale de l’Eclairage (CIE) 2000.
Results and discussion
Unaged commercial acrylic paints
Py–GC/MS results
The results reported here are based on the pyrograms obtained
for each of the acrylic paints using the single-shot and double-
shot techniques. By use of these two methods it was possible
to distinguish three different acrylic binding media:
1. poly(ethyl acrylate/methyl methacrylate), p(EA/MMA);
2. poly(butyl acrylate/methyl methacrylate), p(nBA/
MMA); and
3. poly(2-ethylhexyl acrylate/methyl methacrylate), p(2-
EHA/MMA).
1571
All three acrylic co-emulsions have a characteristic
pyrogram mainly characterised by several specific peaks
related to the monomer units of the polymer itself and their
respective dimers and trimers. Oligomers are formed under
pyrolysis conditions and are usually present in lower
amounts.
The co-emulsion p(EA/MMA) was identified in the
pyrograms of all the Lukas paints (Fig. 1, pyrogram a). The
most intense peak is that of ethyl acrylate (EA) with a
retention time (RT) of 4.3 min and a molecular ion at m/z=
55. The next most intense peak is that of methyl
methacrylate (MMA) monomer (m/z=69) at RT 4.6 min.
Four other peaks were also identified; these corresponded
to an EA-MMA sesquimer (one and a half monomer units)
(m/z=55, 99, 128, and 157), at RT 21.0 min, an EA-MMA
dimer (m/z=67, 95, 140, and 168) at RT 21.8 min, an EA
sesquimer (m/z=55, 87, 143, and 161) at 22.1 min, and an
EA dimer (m/z=53, 98, 126, 154, and 200) at RT 23.1 min.
The EA dimer is the largest peak in this group whereas the
EA sesquimer is the least intense. It was also possible to
detect three EA–EA–MMA trimer peaks (m/z=55, 93, 120,
166, 200, 255, 269, m/z=55, 93, 121, 166, 222, 255, 269,
and m/z=55, 93, 121,167, 200, 227, 268) at RT 31.9, 32.3,
and 33.6 min, and an EA trimer peak (m/z=79, 106, 134,
181, 208, and 355) at RT 33.2 min. Additional peaks from
o-chloroaniline (m/z=65, 92, and 127) at RT 18.0 min and
from o-chlorophenyl isocyanate (m/z=63, 90, 127, and 153)
at RT 18.1 min were noted in the single-shot program
(Fig. 1, pyrogram a, labelled I and II) and in the thermal
desorption double-shot mode pyrogram obtained from the
Lukas green acrylic paint. These two pyrolysis products are
typical of the arylamide yellow pigment (PY 3). Although
characterisation of many azo-pigments by Py–GC/MS
seems to not be problematic, detection of the phthalocya-
nines is challenging, because they do not form scission
products during pyrolysis and are of low volatility [2]. In
fact, the phthalocyanine green pigment (PY 7) listed on the
paint tube of the Lukas green was not detected.
In contrast with these results, a p(nBA/MMA) co-
emulsion was detected in all Liquitex and Rembrandt
samples and in the green Lascaux paint (Fig. 1, pyrogram
b). The most intense peak is related to nBA (m/z=55, 73,
85, and 128) at RT 10.9 min and this is preceded by the
peak of MMA (m/z=69 and 100) at RT 4.6 min. Further-
more, similar to observations for the p(EA/MMA) co-
emulsion in the Lukas samples, several dimer and trimer
peaks were recorded at higher retention times. The first
group of four peaks corresponding to the sesquimers and
dimers could be recognized from characteristic fragment
ions obtained by scission of methoxy or butoxy groups to
give [M − 31]+ and [M − 73]+ cations, because under
electron-impact (EI) ionization the molecular ions are not
detected. The first two peaks at RT 25.3 and 26.0 min were
1572 V. Pintus et al.

Fig. 1 Overall pyrograms

acquired with the single-shot

2-EHA
mode: (a) unaged chromium

2-ethylhexene

2-ethyl hexanol
oxide green from Lukas; (b)
unaged blue ultramarine from

MMA
Liquitex; (c) unaged cadmium
red from Schmincke. Peaks trimers
labelled I and II correspond to sesquimer-dimer
chloroaniline and o-chloro-

Relative intensity
c)
phenyl isocyanate, respectively

nBA
MMA
trimers
sesquimer-dimer
b)
EA trimers
MMA
sesquimer
I II
EMA -dimer
a)

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0
Retention time (min)

identified as an nBA-MMA sesquimer (m/z=55, 73, 115, (m/z=69 and 100) at RT 4.6 min and 2-EHA (m/z=55, 70,
143, and 185) and an nBA-MMA dimer (m/z=57, 67, 95, 112, 127 and 184) at RT 20.07 min, which is the most
112, 126, and 141) whereas the other two peaks at RT 30.0 prominent. Two intense peaks of 2-ethylhexene (m/z=55, 70,
and RT 30.8 min corresponded to an nBA sesquimer (m/z= and 112) at RT 7.0 min and 2-ethylhexanol (m/z=55, 84, and
57, 87, 115, 142, 171, and 189) and an nBA dimer (m/z= 130) at RT 15.2 min are also present. Several other peaks,
57, 98, 127, and 183). The last group of four peaks is made present in the latter parts of the pyrograms, were identified as
up of three nBA–nBA–MMA trimers (m/z=57, 93, 139, dimers and trimers. The first group is composed of four main
195, 250, 283, 325; m/z=57, 93, 120, 167, 195, 250, 283, peaks: 2-EHA/MMA sesquimer (m/z=57, 70, 83, 115, 143,
325; m/z=57, 93, 121, 167, 195, 228, 283, 296) at RT 37.0, 185, and 241) at RT 31.6 min, 2-EHA/MMA dimer (m/z=57,
38.0, and 39.4 min and, with the most intense peak, an nBA 70, 95, 112, 127, 141, 197, 225, and 284) at RT 32.1 min, 2-
trimer (m/z=57, 109, 134, 181, 208, 236, 282, and 311) at EHA sesquimer (m/z=57, 71, 83, 115, 133, 155, 227, 245,
RT 41.3 min. It was also possible to detect a marker peak of 284, 327, and 357 ) at RT 40.3 min, and 2-EHA dimer (m/z=
a non-ionic surfactant, for example octyl phenyl polyethoxy
ethanol, after thermal desorption of all Liquitex specimens
with the double-shot mode (Fig. 2, pyrograms a and b). m/z 135
d)
Small concentrations of this polyethoxylated-type surfac- TIC
tant are often present in recent paint formulations. Its c)
Relative intensity

detection with Py–GC/MS is quite challenging, because its m/z 135

marker peaks may partially or totally overlap with those of b)
other components and hardly any studies on it have been
done so far [2, 3]. No pyrolysis fragments of the non-ionic
surfactant were evident in the total ion chromatogram and TIC
only by plotting the single ion mass profiles at m/z=135 a)
from the thermal desorption was octylphenol (m/z=135, 0 10 20 30 40
206) detected. This is a marker compound of alkylaryl Retention time (min)
polyethoxylates for the non ionic surfactant octyl phenyl
Fig. 2 Identification of an octyl phenyl polyethoxy ethanol surfactant
polyethoxy ethanol [2]. in Liquitex cadmium red, p(nBA/MMA) acrylic emulsion: (a) total
The blue, red, and green paints from Winsor & Newton ion chromatogram (×100,000) of the unaged sample analysed in the
and from Schmincke and the blue and red paints from Lascaux double-shot mode, thermal desorption; (b) single ion mass profile at
m/z 135, a marker ion fragment of octylphenol; (c) total ion
are mainly based on a co-emulsion of poly(2-ethylhexyl
chromatogram (×100,000) of the sample analysed in the double-shot
acrylate/methyl methacrylate), p(2-EHA/MMA) (Fig. 1, pyro- mode after 83 days of UV ageing, thermal desorption; (d) single ion
gram c). The two most intense peaks are those from MMA mass profile at m/z 135, a marker ion fragment of octylphenol
Evaluation of lightfastness declarations of acrylic paints
57, 71, 112, 127, 145, 181, 257, 281, 311, and 369) at RT
40.9 min. The last group is of three intense peaks: 2-EHA–2-
EHA–MMA trimers (m/z=57, 93, 139, 195, 257, 269, 324,
368, 381, 436, and 469; and m/z=57, 93, 139, 195, 226, 257,
269, 306, 338, 381, 436, and 469) at RT 45.5 and 45.8 min
and an e-EHA trimer (m/z=57, 93, 149, 167, 227, 284, 325,
368, 439, 469, and 553). Similar to the Liquitex samples,
octylphenol was detected in the thermal desorption pyrogram
acquired in the double-shot mode from the green Schmincke
paint film, by plotting the corresponding single ion mass
profile at m/z=135.
FTIR–ATR results
The FTIR–ATR absorption of all the acrylic paint products
investigated are summarized in Table 2. Depending on the
type of acrylic binding medium, the types of surfactant, and
the presence of different extenders, characteristic similarities
and differences in the infrared absorption of the samples are
listed. Because of the pronounced absorption of the acrylic
binding media, and the surfactants, the presence of extenders
was not obvious in each spectrum and only a few of their
characteristic peaks could be observed. Furthermore, the
presence of phthalocyanine green (PG 7), arylamide yellow
(PY 3), and synthetic yellow ochre (PY 42) in the green Lukas
sample, as indicated on the paint tube by the colour index
generic name (C.I. name), were not all detected. The FTIR–
ATR results are summarized below and arranged according to
the corresponding compound types, i.e.:
1. acrylic binding media and surfactant; and
2. extender and pigment.
Acrylic binding media and surfactant
OH stretching (3,600–3,100 cm−1) All acrylic paint for-
mulations had broad, indistinct absorption between 3,600
and 3,100 cm−1 with a maximum peak at 3,400 cm−1
corresponding to different hydroxylic structures.
C–H stretching (3,100–2,800 cm−1) In the spectra of the
ultramarine blue, cadmium red, and hydrated chrome oxide
green paints from Winsor & Newton and from Schmincke,
and the blue and red from Lascaux the main C–H stretching
frequencies were observed at 2,952 and 2,927 cm−1 com-
plemented by two smaller peaks at 2,872 and 2,858 cm−1. In
contrast, the spectra of all Liquitex and Rembrandt paints
and Lascaux chromium oxide green had two peaks at 2,953
and 2,930 cm−1 and a smaller one at 2,873 cm−1. The main
absorption peaks of the polyethoxylated non-ionic surfactant,
in the Lukas acrylic paints, corresponded to 2,890 cm−1, and
was accompanied by three less intense peaks at 2,980, 2,740,
and 2,694 cm−1.
1573
C=O stretching (1,750–1,700 cm−1) In the spectra of all the
paints from all the companies, the carbonyl stretching
absorption occurs at a similar wavelength between
1,729 cm−1 (Lascaux) and 1,724 cm−1 (Liquitex).
A broad weak band at 1,567 cm−1 was noticed in the
spectra from Winsor & Newton and Liquitex paint films;
this is likely to correspond to the COO asymmetric
stretching vibrations related to metal carboxylate complexes
[29]. This band suggests the presence of a poly(acrylic)
type thickener or an anionic surfactant with the non-ionic
PEO type to improve the electrostatic stabilization of the
inorganic pigment in the emulsion [29, 32].
C–H bending (1,500–1,300 cm−1) The spectra of the Winsor
& Newton, Liquitex, Rembrandt, and Schmincke paint films,
and the Lascaux ultramarine blue sample have a double peak at
1,449 and 1,435 cm−1 complemented by another less intense
peak at 1,384 cm−1. The Lukas blue and green acrylic paints
have a doublet at 1,467 and 1,446 cm−1 and another small
peak at 1,381 cm−1. Additionally two other peaks related to
the polyethoxylated non-ionic surfactant were detected in the
Lukas samples and in the Liquitex red and green samples: the
most intense at 1,343 cm−1 and a smaller peak at 1,361 cm−1.
C–O and C–C stretching vibrations (1,250–900 cm−1) In
this frequency region the most intense peak at 1,140 with a
shoulder at 1,165 cm−1 was observed in the Winsor & Newton
and the Schmincke paint films, and in the Lascaux blue and
red samples with another less intense peak at 1,237 cm−1. The
spectra of the Liquitex and Rembrandt acrylic paints and the
green Lascaux contained a double peak at 1,159 and
1,143 cm−1 and another small peak at 1,238 cm−1 accompa-
nied by two small peaks at 1,117 and 1,065 cm−1. Addition-
ally, a peak at 989 cm−1 was detected in the spectra of the
Winsor & Newton, Liquitex, Rembrandt, Lascaux, and
Schmincke red and green samples. In the spectra of all the
red and green acrylic paints, the most visible peak of the
surfactant was at approximately at 963 cm−1 accompanied by
other characteristic peaks depending on the companies: at
942 cm−1 (Rembrandt) and at 1,108 and 1,061 cm−1 (Lukas).
C–H rocking vibrations (900–600 cm−1) All the spectra
contained C–H rocking frequencies at 752 cm −1 .
Concerning the polyethoxylated non-ionic surfactant, the
main absorption in the spectra obtained from all the acrylic
paints was in the region of 842 cm−1.
Extenders and pigments
Kaolinite (Al2Si2H4O9) Kaolinite, also called china clay, is
a hydrated aluminum silicate and was observed in the
Liquitex, Rembrandt, Lascaux, and Schmincke blue speci-
Table 2 ATR infrared absorption of the commercial acrylic paints investigated and component assignments
1574

Bond type Lascaux p(2-EHA/MMA) p Liquitex p(nBA/ Lukas p(EA/ Rembrandt p(nBA/ Schmincke p(2-EHA/ Winsor & Newton p(2- Compound type
(nBA/MMA) (cm−1) MMA) (cm−1) MMA) (cm−1) MMA) (cm−1) MMA) (cm−1) EHA/MMA) (cm−1)

(Stretching vibrations) 3,692, 3,666, 3,647, 3,620 3,693, 3,649, 3,694, 3,666, 3,693, 3,666, 3,649, 3,692, 3,666, 3,649, Kaolinite extender (LIQ blue, REM
3,619 3,647, 3,619 3,619 3,618 blue, LAS blue, SCH blue)
– – – – 3,674 – Talc (SCH red)
O–H stretching 3,400 3,400 3,400 3,400 3,400 3,400 Hydroxylic structures
C–H stretching – – 2,980 – – – Acrylic binder
2,953, 2,928 2,953, 2,930 2,952 2,952, 2,930 2,953, 2,931 2,952, 2,927 Acrylic binder
– – 2,917, 2,890 – – – Polyethoxylated non-ionic surfactant
2,873, 2,860* 2,873 2,861 2,873 2,872, 2,861 2,872, 2,858 Acrylic binder
– – 2,740, 2,694 – – – Polyethoxylated non-ionic surfactant
(Stretching vibrations 2,513, 1,796 – 2,517, 1,796 2,515, 1,796 – – Calcium carbonate extender (REM
carbonate groups) red, LUK blue, LAS red and green)
C=O stretching 1,729 1,724 1,726 1,726 1,726 1,727 Acrylic binder
– – 1,671, 1,593, – – – Arylamide yellow (PY 3)
1,584
– – 1,565 – – – Phthalocyanine green (PG 7)
– – 1,537, 1,503 – – – Arylamide yellow (PY 3)
– 1,564 – – – 1,567 Metal-carboxylate
C-H bending – 1,466 1,467 – – – Acrylic binder, polyethoxylated non-
ionic surfactant (LIQ red and
green, LUK all)
1,450, 1,435 1,448, 1,435 1,446 1,449 1,451, 1,435 1,449, 1,435 Acrylic binder (LUK red and
green, LAS blue)
(Stretching vibrations 1,418, 1,395 – 1,431 – – – Calcium carbonate (LUK blue)
carbonate groups) 1,384 1,384 1,381 1,385 1,384 1,384 Acrylic binder (LUK red and green)
– 1,361 1,361 – – – Polyethoxylated non-ionic surfactant
(LIQ red and green, LUK all)
– 1,343 1,342 – – – Polyethoxylated non-ionic surfactant
(LIQ red and green, LUK all)
C–O and C–C stretching – 1,272 shoulder 1,280 – – – Polyethoxylated non-ionic surfactant
(LIQ red and green, LUK all)
1,236 1,238 1,240 1,236 1,237 1,237 Acrylic binder
1,161 1,159 – 1,158 1,165 1,165 shoulder Acrylic binder
1,142 1,143 1,148 1,141 1,142 1,140 Acrylic binder
1,118 1,114 1,108 1,117 – – Polyethoxylated non-ionic
surfactant (LAS green)
1,065 1,062 1,061 1,065 – – Acrylic binder/polyethoxylated (LIQ
and REM red and green, LAS green)
– – – – 1,069 1,072 Barite extender (W&N red, SCH green)
(Stretching vibrations) – – 1,033 – – – Kaolinit extender (LUK red and green)
– 1,022 shoulder – 1,022 shoulder – – Acrylic binder
V. Pintus et al.
Table 2 (continued)
Bond type Lascaux p(2-EHA/MMA) p Liquitex p(nBA/ Lukas p(EA/ Rembrandt p(nBA/ Schmincke p(2-EHA/ Winsor & Newton p(2- Compound type
(nBA/MMA) (cm−1) MMA) (cm−1) MMA) (cm−1) MMA) (cm−1) MMA) (cm−1) EHA/MMA) (cm−1)

– – – – 1,013 – Talc (SCH red)

989 989 – 990 988 989 Acrylic binder in red and green paints
– – 982 – 983 984 Barium sulfate extender (W&N red,
LUK all, SCH green)
(Stretching vibration 981 979 1,025, 1,006 978 977 980 Ultramarine blue
silicate) 963 963 963 963 963 964 shoulder Polyethoxylated non-ionic surfactant
in red and green paint
– – – 942 – – Polyethoxylated non-ionic surfactant
in red and green paint
(Stretching vibrations 872 – 873 873 – – Calcium carbonate extender (REM red, LUK
carbonate groups) blue, LAS red and green)
C–H rock 847 842 844 844 841 844 Acrylic binder, polyethoxylated non-
ionic surfactant
Evaluation of lightfastness declarations of acrylic paints

752 750 750 752 752 752 Acrylic binder

(Stretching vibrations 711 – 713 713 – – Calcium carbonate extender (REM
carbonate groups) red, LUK blue, LAS red and green)
(Stretching vibration 691, 656 689, 654 – 689, 655 690, 656 688, 654 Ultramarine blue
silicate) – – – – 668 – Talc extender (SCH red and green)
(Stretching vibration – – 633, 607 – 635, 609 632, 608 Barite extender (W&N red, LUK green)
sulfate)
(Stretching vibration 615, 556 608, 524 – 609, 525 – 611, 540 Chromo oxide green (PG 17)
oxide) – – – – 550, 472 – Chromo oxide green (PG 18)

LAS, Lascaux; LIQ, Liquitex; LUK, Lukas; REM, Rembrandt; SCH, Schmincke; W&N, Winsor & Newton
a
Acrylic co-emulsion in the blue and red specimens
b
Acrylic co-emulsion in the green specimen
1575
1576
mens and in the Lukas paints as four distinctive peaks. The
two most prominent were at 3,693 and 3,619 cm−1 and two
less intense peaks were at 3,666 and 3,649 cm−1. Further
attribution to kaolinite is because of the peak at 1,033
present in the Lukas red and green acrylic paints.
Calcite (CaCO3) Calcium carbonate was identified in the
red and green Rembrandt and Lascaux paints, and in the
blue Lukas paint. Two small characteristic peaks of calcium
carbonate were detected at 2,515 and 1,796 cm−1 and a
strong and broad absorption in the frequency region
between 1,400 and 1,500 cm−1 with a maximum at
1,434 cm−1. Moreover, a sharp peak at 873 cm−1 was
present together with a less intense peak at 713 cm−1.
Barite (BaSO4) Barium sulfate, with characteristic high
absorption between 1,050 and 1,250 cm−1 and less intense
absorption between 610 and 640 cm−1, was detected in all
the Lukas specimens, in the Schmincke green, and in the
Winsor & Newton red samples. Because of the main
absorption of the acrylic binding media, in each case the
most visible peaks corresponded to two weak but sharp
peaks at approximately 608 and 632 cm−1.
Talc (Mg3(Si4O10)(OH)2) Also known as hydrated magne-
sium silicate, talc gives three sharp peaks, the highest
around 3674 cm−1 and the smaller two at 1013 and
668 cm−1. All three peaks were found only in the red
Schmincke paints.
Ultramarine blue (Na8Al6Si6O24.Sx), PB 29 The spectra
from the blue paints from all the companies contained the
overlapping stretching bands for Si–O–Si and Si–O–Al
between 1,150 and 950 cm−1, interfering with the C–O/C–
C skeletal vibrations (900–1,250 cm−1) region of the acrylic
binding media. Moreover, a typical weaker area of
absorption with distinct peaks at 688 and 654 cm−1 was
observed.
Chromium oxide green (Cr2O3), PG 17, and hydrated
chromium oxide green, PG 18 The spectra from the
chromium oxide green pigments PG 17 and PG 18 have
characteristic absorption bands in the region 550–230 cm−1
[33]. PG 17, with broad doublet peaks around 610 and
525 cm−1, was present in all the green paints except that
from Lukas. On the other hand, hydrated chromium oxide
green PG 18, which is present in the Schmincke sample,
has a broad absorption band in the OH stretching region
(3,600–3,100 cm−1) followed by broad doublet peaks at
550 and 472 cm−1.
Phthalocyanine green (C32H3N8Cl13Cu), PG 7 The FTIR
spectra of organic pigments are usually characterised by
V. Pintus et al.
many sharp and broad peaks, especially in the region
between 1,680 and 730 cm−1. The only recognizable peak
in the spectra from the green Lukas sample was at
1,565 cm−1 probably because of the presence of only small
amounts of the phthalocyanine green pigment.
Arylamide yellow, PY 3 With characteristic strong absorp-
tion in the region between 1,680 and 1,400 cm−1, the
arylamide yellow pigment was observed in the green Lukas
specimen with three sharp peaks at 1,671, 1,533, and
1,507 cm−1 followed by doublet peaks at 1,593 and
1,584 cm−1.
Synthetic yellow ochre (Fe2O3.H2O), PY 42 No typical
absorption peaks at 802 and 912 cm−1 of synthetic yellow
ochre were detected.
Colour measurement results
The reflectance spectra of the acrylic paints corresponded to
those of the pigments, which are part of the product
according to the generic colour index labels on the paint
tubes. Identification of the surfactants was not possible
because their absorption is usually in the lower UV regions.
The colour measurement results for the commercial acrylic
paints are presented below and arranged according to the
three colours investigated.
Blue The ultramarine blue pigment, PB 29, present in all
the blue paints, has a characteristic spectrum in the region
between 380 and 520 nm with a maximum reflectance band
at approximately 460 nm. The Rembrandt blue had the
highest reflection value of 0.38 (Fig. 3) whereas the Winsor
& Newton blue had the lowest (0.21).
Green The green paints of Winsor & Newton, Liquitex,
Rembrandt, and Lascaux (Fig. 3) containing the chromi-
um oxide green pigment PG 17 had typical reflectance
spectra with two bands, the most prominent with a
maximum at 540 nm and a weaker band at 410 nm. In
contrast, the reflectance spectrum of the green paint from
Schmincke containing the hydrated chromium oxide green
PG18 had a major band with a maximum at 510 nm
(Fig. 3). The green Lukas paint, which is made with a
mixture of four different pigments (PG 17, PG 7, PY 3,
and PY 42) had a reflectance spectrum with a unique band
at 530 nm, which seems to arise from the phthalo green
pigment, PG 7 (Fig. 3). Identification of the yellow
pigments by fingerprinting their absorption characteristics
is challenging, because their main absorption is in the
short-wavelengths of the violet region and because of their
reflection of all other wavelengths [34].
Evaluation of lightfastness declarations of acrylic paints
Fig. 3 Reflectance spectra of 1
the Lukas, Schmincke, and
Winsor & Newton red paints, 0,9
the Rembrandt blue sample, and
0,8
the Lascaux, Lukas, and
Schmincke green paints 0,7
0,6
Reflectance
0,5
0,4
0,3
0,2
0,1
0
380 410
Red The reflectance spectrum of the red acrylic Schmincke
paint, containing a cadmium orange pigment, PO 20,
appears flat throughout the violet region and into the green
(Fig. 3). The red samples from Winsor & Newton (Fig. 3),
Liquitex, Rembrandt, and Lascaux containing cadmium red
medium, PR 108, had reflectance spectra almost identical
with that of the Schmincke red, with the characteristic
flatness of the cadmium red pigment in the same region.
The mixture of PR 108 and PO 20 in the Lukas red acrylic
paint had slight absorption in the lower green wavelength
region, in contrast with the other red samples (Fig. 3).
Aged commercial acrylic paints
To evaluate the lightfastness of the blue, green, and red
acrylic paints, each colour was analysed after UV exposure
(31 and 83 days) in the same way as before ageing
(discussed in the section “Unaged commercial acrylic
paints”). Even after the first ageing period, some of the
samples had visually changed colour slightly and had
different opacity. In addition, while scraping samples from
the aged films for Py–GC/MS analysis, it was observed
they had become more fragile and brittle than unaged paint
films. These changes in their macroscopic properties can be
regarded as characteristic for UV ageing. Comparison of the
results obtained from unaged and aged (31 and 83 days)
samples clearly reveals that the effect of the photo-oxidative
reactions was substantially stronger after 83 days of UV
exposure.
Py–GC/MS results
Blue In general, comparison of the pyrograms recorded in
the single-shot mode for unaged and aged blue samples did
1577
Red Lukas®
Red Schmincke®
Red Winsor & Newton®
Blue Rembrandt ®
Green Lascaux ®
Green Lukas®
®
Green Schmincke
440 470 500 530 560 590 620 650 680 710
Wavelength nm
not reveal significant differences, even after 83 days of UV
exposure. In contrast, the results from thermal desorption
after UV exposure revealed, in some cases, noticeable
changes. The thermal desorption results for the Lascaux
blue paint (***, lightfast, which indicates only moderate
UV resistance) were not detectably different after UV
exposure. The Lukas blue paint, although labelled with
the same lightfastness index (***) as Lascaux blue, was the
most sensitive blue paint, and in the thermal desorption
pyrogram new volatile compounds and new products,
which could be formed during the photo-oxidative process-
es, were observed at high retention times. For instance,
low-intensity peaks of (hexadecyloxy)methyloxirane (m/z=
57, 97, and 125) at RT 41.7 min, 1,2:7,8-diepoxyoctane (m/
z=55 and 97) at RT 46.1 min, and sulfurous acid, dodecyl
2-propyl ester (m/z=57, 85, 135, and 160) at RT 46.8 and at
RT 48.0 min were detected (Fig. 4, pyrograms a and b).
Another consequence of UV ageing is the early production
and detection of dimers, sesquimers, and trimers in the
thermal desorption pyrograms, which were not detected in
the unaged material. The photo-ageing processes have
evidently changed the thermal stability of the sample with
consequent production of oligomers even during the
thermal desorption [3]. Peaks related to oligomers, fol-
lowed by several small peaks of photo-oxidation products
(e.g. (hexadecyloxy)methyloxirane and sulfurous acid,
dodecyl 2-propyl ester, were also found after thermal
desorption of the Liquitex (I, excellent) (Fig. 4, pyrograms
c and d) and Rembrandt (+++, excellent). Another
indication of photo-oxidative alterations is related to the
octylphenol surfactant in the Liquitex sample, which was
detected in the single ion mass profile obtained after
thermal desorption in the double-shot mode, at m/z=135,
in the unaged sample, but almost no traces were found in
the pyrogram of the aged material.
1578 V. Pintus et al.

2.00 (x1,000,000)

1.75 trimers
d)

1 3 4
1.50
c)
Relative intensity

1.25

1.00 trimers b)

0.75

1 23 4
0.50
a)
0.25

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0
Retention time (min)

Fig. 4 Overall pyrograms of the blue Lukas sample containing p(EA/ Liquitex sample analysed in the double-shot mode, thermal desorp-
MMA) and the Liquitex sample containing p(nBA/MMA): unaged (a) tion. Peaks: 1, oxirane, [(hexadecyloxy)methyl] (m/z=57, 97, and
and aged for 83 days (b) Lukas sample analysed in the double-shot 125); 2, 1,2:7,8-diepoxyoctane (m/z=55, and 97); 3 and 4, sulfurous
mode, thermal desorption; and unaged (c) and aged for 83 days (d) acid, dodecyl 2-propyl ester (m/z=57, 85, 135, and 160)

Green Similar to the results for the blue samples, the single-
shot pyrograms of the green paints before and after UV
exposure did not reveal noticeable differences. In contrast, the
double-shot mode revealed the effects of photo-oxidative
reactions especially in the Lukas green paint (***, lightfast).
Additionally, near several closely spaced small peaks, starting
at a high retention time (approximate RT 45 min) and
connected with oxidation products (Fig. 5b), another two
peaks related to spirohexane-1-carboxylic acid, ethyl ester
(m/z=80, 98, 122, 155, and 196) at RT 23.1 min and to 3-
(acetyloxy)cyclohexyl acetate (m/z=80, 103, 145, and 200)
at RT 23.4 min were observed (Fig. 5a). All the other green
paint samples were quite UV resistant, because no oxidation
products and oligomers were present in their thermal
desorption pyrograms. It is interesting to note that for the
Lascaux green paint with the lowest lightfastness index (**,
limited lightfast) the pyrogram obtained with the double-shot
mode did not show any differences. Similar to the Liquitex
blue paint mentioned above, only a small peak
corresponding to octylphenol was observed when plotting
the corresponding single ion mass profile at m/z=135 in the
thermal desorption pyrogram of the Liquitex green and
Schmincke green paints, and there was a notable reduction in
the peak area in the aged samples of both of the green paints.

a) (x100,000) b) (x100,000)
1.50
1.00
1.25
Relative intensity

0.75 I II 1.00
III V IV
0.75 IV
0.50
0.50
0.25
0.25

22.0 22.5 23.0 23.5 24.0 24.5 45.0 46.0 47.0 48.0 49.0
Retention time (min) Retention time (min)

Fig. 5 a, b Detail of pyrograms of the Lukas green sample containing and 196); II, 3-(acetyloxy)cyclohexyl acetate (m/z=80, 103, 145, and
p(EA/MMA). Unaged (solid line) and aged for 83 days (dashed line) 200); III, 1,2,7,8-diepoxyoctane (m/z=55 and 97); IV, (dodecyloxy)
analysed in double-shot mode, thermal desorption. Peaks: I, methyloxirane (m/z=57, 97, and 125); andV, 7-Oxabicyclo[4.1.0]
spirohexane-1-carboxylic acid, ethyl ester (m/z=80, 98, 122, 155, heptane, 3-(epoxyethyl) (m/z=79, 95, and 121)
Evaluation of lightfastness declarations of acrylic paints
Red The single-shot pyrograms of unaged and UV-aged red
acrylic paints also were not noticeably different. With the
exception of the Liquitex red paint, even the thermal
desorption pyrograms obtained by use of the double-shot
mode after UV ageing did not show detectable volatile
compounds or oxidation products. The non-ionic octyl
phenyl polyethoxy ethanol surfactant which was found in
the thermal desorption pyrogram of the unaged Liquitex red
paint could not be detected after 83 days of UV ageing
(Fig. 2, pyrograms c and d).
FTIR–ATR results
Significant changes in the IR spectra were documented for
the UV-aged blue acrylic paints; the red samples were the
most stable materials.
Blue In contrast with its lightfastness declaration (***,
lightfast), indicating only a moderate UV stability, the IR
spectra of the Lascaux blue paints revealed no detectable
alterations after UV exposure, in agreement with its Py–GC/
MS results. The Lukas blue paint, although having the same
lightfastness index as the Lascaux blue, was the most
sensitive. The changes were mainly characterised by total
reduction of the PEO non-ionic surfactant peaks (2,917,
2,890, 2,740, 2,694, 1,467, 1,361, 1,343, 1,280, 1,108,
1,061, and 963 cm−1) even after 31 days of UV ageing
(Fig. 6). Furthermore, the doublet peaks at 2,980 and
2,952 cm−1, related to the CH stretching vibration, were
more visible when the absorption of the surfactant
decreased. For the other blue samples—Winsor & Newton
(I, excellent), Liquitex (I, excellent), Rembrandt (+++,
excellent) (Fig. 7), and Schmincke (****, good lightfast-
ness)—all with higher lightfastness declarations than Lukas
Fig. 6 FTIR–ATR spectra of the
0.7
Lukas blue paint containing p
(EA/MMA) before ageing
0.6
(black line) and after UV ageing
for 31 (red line) and 83 (green
0.5
line) days
ATR Units
0.4
0.3
0.2
3694
0.1
0.0
3500
1579
and Lascaux, the changes were comparable. Absorption of
the carbonyl peak at 1,726 cm−1 gradually decreased after
31 and 83 days of UV ageing, which can be related to the
loss of ester groups such as butyl and 2-ethylhexyl groups.
Additionally, broadening of the carbonyl band with pro-
gressive growth of the absorption at 1,788 cm −1 ,
corresponding to the formation of a γ-lactone structure
which absorbs at 1,780 cm−1 [25, 28, 35] or to the
formation of open chain anhydrides which absorb at
1,800 cm−1 [36], took place gradually even after 31 days
of UV ageing. Other evidence of photo-oxidative reactions
is given by a gradual decrease in the absorption of the peak
at 2,930 cm−1 in the IR spectra of Liquitex and Rembrandt
blue samples (Fig. 7) related to the –CH2 asymmetric
stretching vibration of the acrylic binder and probable loss
of ester groups.
Green In contrast with the results obtained for the blue
samples, the IR spectra of the green acrylic paints did not
reveal significant modifications apart from for the Liquitex
green (I, excellent) and Lukas green (***, lightfast) paints.
The different behaviour of the Liquitex green (Fig. 8) and
Lukas green paints were mainly the gradual decrease of the
PEO-type surfactant absorption after 31 and 83 days of UV
ageing—at 1,343 and 1,114 cm−1 for the Liquitex green
sample and at 2,917, 2,890, 2,740, 2,694, 1,467, 1,361,
1,343, 1,280, 1,108, 1,061, and 963 cm−1 for the Lukas
green paint. In addition, the metal-carboxylate peak of the
Liquitex green paint at 1,564 cm−1 also decreased gradually.
This result indicates that the metal–surfactant complexes of
the carboxylate type are sensitive to UV ageing. The
progressive broadening of the carbonyl band in the
frequency region between 1,830 and 1,730 cm−1 of the
Lukas green sample is similar to the changes noted for the
aged blue paints mentioned above.
1726 1108
1431
2890
963
1342 873
607
2952
2980
3000 2500 2000 1500 1000 500
Wave number cm-1
1580 V. Pintus et al.

Fig. 7 FTIR–ATR spectra of the

Rembrandt blue paint containing 1726
978
p(nBA/MMA) before ageing

0.4
(black line) and after UV ageing
for 31 (red line) and 83 (green
line) days

0.3
ATR Units
1158
2952
2930 689 655

0.2
2873
3694
1449

0.1
0.0
3500 3000 2500 2000 1500 1000 500
Wave number cm-1

Red The red acrylic paints seem to be particularly stable.
With the exception of the Liquitex red (I, excellent) and
Lukas red (***, lightfast) paints (Fig. 9) no significant
differences between the unaged and aged films could be
determined. Similar to the blue and green paints from
Liquitex and Lukas, total reduction of the absorption of the
PEO-type surfactant peaks was observed in both of the
paints after 31 days of UV ageing. For the Liquitex red
paint, the sharp peaks at 1,343 and 1,114 cm−1 disappeared
whereas for the Lukas red paint the peaks at 2,917, 2,890,
2,740, 2,694, 1,467, 1,361, 1,343, 1,280, 1,108, 1,061, and
963 cm−1 disappeared. For the Lukas red sample, the
decrease of the surfactant absorption was accompanied by
an increase in the absorption of the kaolinite extender.
Similar to the changes in the Winsor & Newton blue,
Liquitex blue, Rembrandt blue, Schmincke blue, and Lukas
green paint films, the carbonyl band broadened with a
progressive increase in the absorption at 1,788 cm−1,
corresponding to the formation of a γ-lactone structure or
to the formation of open-chain anhydrides after 83 days of
UV ageing. Moreover, the region between 1,560 and
1,710 cm−1 is of particular interest, because it is related to
the formation of unsaturated molecules with a C=C bond or
to the formation of ketones. Gradual formation of ketone
was also apparent in the IR spectra of the aged Liquitex red
films, and was complemented by a decrease of the metal–
carboxylate peak at 1,564 cm−1. In the IR spectrum of the
Winsor & Newton red sample the peak at 1,567 also
disappeared completely after 83 days of UV ageing.
Colour measurement results
Table 3 summarizes the colour changes of all the investigated
unaged and aged (83 days) acrylic paints, including the shift in
the values of the lightness/darkness (L*), redness/greenness

Fig. 8 FTIR–ATR spectra of the

Liquitex green paint containing 1724
0.6

p(nBA/MMA) before ageing

(black line) and after UV ageing
0.5

for 31 (red line) and 83 (green

line) days
0.4
ATR Units

1114
2953 2930
0.3

2873 1448
1343 608
0.2
0.1
0.0

3500 3000 2500 2000 1500 1000 500

Wave number cm-1
Evaluation of lightfastness declarations of acrylic paints 1581

Fig. 9 FTIR–ATR spectra of the

Lukas red paint containing p 1726 1108
2890

0.6
(EA/MMA) before ageing
(black line) and after UV ageing
for 31 (red line) and 83 (green

0.5
line) days 963
2952

ATR Units
0.4
1342
1280
3694 2980

0.3
1467 607
844

0.2
0.1
0.0
3500 3000 2500 2000 1500 1000 500
Wave numbercm-1

(a*), yellowness/blueness (b*), and total colour (E*) [34]. Blue The Rembrandt (***, lightfast), Winsor & Newton
Especially, in the CIELAB diagram shown in Fig. 10 it is (I, excellent), Liquitex (I, excellent), and Lukas (***,
possible to see the differences in the a* and b* values of the lightfast) blue acrylic paints had the greatest shift of a*
unaged and aged paints of each colour, indicating colour and b* values between unaged and aged samples. These
changes. The differences in L* correspond to the brightening shifts indicate a reduction in red for Rembrandt, Winsor &
and darkening of the paint films because of UV exposure. Newton, and Lukas, whereas for Liquitex the reduction in
Generally, the results show that the blue acrylic paints are red was only slight. All of these four brands shifted toward
more sensitive to UV light than the green and red. blue during UV ageing except Rembrandt, which became
much more yellow (Table 3, Fig. 10). In contrast, for the
Lascaux (***, lightfast) blue sample there was a slight
Table 3 Shifts in the L*, a*, b*, and E* coordinates of the acrylic increase in the a* and b* coordinates corresponding to an
paints before and after 83 days of UV ageing increase of the red and yellow components. The L* values
Acrylic paint film ΔL* Δa* Δb* ΔE* of the Winsor & Newton, Liquitex, and Lukas samples
increased after 83 days of UV ageing, indicating an increase
Blue of their brightness (Table 3, Fig. 10). This can be explained
Lascaux −4.96 1.21 1.49 3.71 by smoothing of the film surfaces during UV exposure [29].
Liquitex 5.53 −1.08 −10.26 7.08 In the Lascaux blue sample a lower L* value, ΔL*=−4.96
Lukas 9.49 −4.83 −3.61 9.22 was observed, indicating darkening. Similar behaviour in
Rembrandt −5.59 −7.13 15.67 6.29 the L* value was observed for the Rembrandt (+++,
Schmincke −3.14 −0.58 −0.94 2.35 excellent) and Schmincke (****, good lightfastness) blue
Winsor & Newton 5.96 −4.49 −5.58 6.39 samples, whereas the changes in the a* and b* coordinates
Green indicated a shift to the blue component of the colour. The
Lascaux 1.93 2.04 −2.01 2.28 Schmincke blue paint was the most stable blue acrylic paint
Liquitex 2.24 2.33 −2.37 2.55 material.
Lukas −1.03 4.78 −8.32 3.17
Rembrandt 2.90 2.08 −1.45 3.09 Green The colour measurements of the unaged and aged
Schmincke 2.08 −0.74 1.42 1.93 green paint samples were indicative of substantially less
Winsor & Newton 0.33 0.85 −0.55 0.58 pronounced colour changes than for the blue acrylic paints.
Red For the Liquitex (I, excellent), Rembrandt (+++, excellent),
Lascaux 0.44 −1.36 −1.27 0.71 Lascaux (**, limited lightfast), and Lukas (***, lightfast)
Liquitex 1.58 −3.03 −6.81 2.84 green paints a small increase in the a* coordinate (more
Lukas 0.81 −2.43 −4.11 1.65
red) and a slight decrease of the b* coordinate (more blue)
Rembrandt 1.65 −2.38 −4.49 2.28
were observed (Table 3, Fig. 10). The greatest shift in the
Schmincke 0.53 −1.92 −4.48 1.66
a* and b* coordinates was for the Lukas green sample. This
large shift, in comparison with all other green samples
Winsor & Newton 0.53 −0.41 −2.00 0.95
which contain inorganic green pigments, might be
1582 V. Pintus et al.

yellow
bright b*+
L* 60

Winsor &N ewton®

70
50

Rembrandt®
Schmincke®
40
Lascaux®
Liquitex®
60 Lukas®

30

50 20

10

40
a*- a*+
green -50 -40 -30 -20 -10 10 20 30 40 50 60 70 red
-10
30
-20

-30
20
-40

10 -50

-60

0 -70
dark b*-
blue
® ® ®
Lascaux Blue (***) Lascaux Green (**) Lascaux Red (***)
® ®
Lascaux Blue (***) aged Lascaux Green (**) aged Lascaux® Red (***) aged
Liquitex® Blue (I) Liquitex® Green (I) Liquitex® Red (I)
Liquitex® Blue (I) aged Liquitex® Green (I) aged Liquitex® Red (I) aged
® ® ®
Lukas Blue (***) Lukas Green (***) Lukas Red (***)
® ® ®
Lukas Blue (***) aged Lukas Green (***) aged Lukas Red (***) aged
Rembrandt® Blue (+++) Rembrandt® Green (+++) Rembrandt® Red (+++)
Rembrandt® Blue (+++) aged Rembrandt® Green (+++) aged Rembrandt® Red (+++) aged
® ®
Schmincke Blue (****) Schmincke Green (*****) Schmincke® Red (*****)
® ®
Schmincke Blue (****) aged Schmincke Green (*****) aged Schmincke® Red (*****) aged
Winsor & Newton® Blue (I) Winsor & Newton® Green (I) Winsor & Newton® Red (I)
® ® ®
Winsor & Newton Blue (I) aged Winsor & Newton Green (I) aged Winsor & Newton Red (I) aged

Fig. 10 CIELAB diagram of the commercial acrylic paints investigated before and after UV ageing for 83 days showing the shifts of their L*, a*,
and b* coordinates

explained by the presence of two organic pigments, which Conclusions

are possibly more sensitive to UV exposure. The Winsor &
Newton green (I, excellent) paint was least sensitive to UV
exposure (Table 3, Fig. 10).
Red The colour results for the red acrylic paints changed
substantially less than for the blue and green samples after
UV exposure. For all the red paints a consistent slight
decrease in the a* and b* coordinates was observed,
resulting in a shift toward blue and green (Table 3,
Fig. 10). The Winsor & Newton (I, excellent) and Lascaux
(***, lightfast) red paints were the most stable. The relative
stability of the red paints was also confirmed by the similar
L* values for unaged and aged samples.
Specific differences in UV sensitivity and stability were
observed during UV-ageing under simulated outdoor con-
ditions of three commercial acrylic colours (cadmium red,
ultramarine blue, and chromium oxide green) from six
different manufacturers. Three different types of acrylic
emulsion were identified by Py–GC/MS analysis of the
commercial acrylic paints: poly(ethyl acrylate/methyl meth-
acrylate) copolymer, p(EA/MMA), in all the Lukas sam-
ples, poly(n-butyl acrylate/methyl methacrylate) copolymer,
p(nBA/MMA), in all the Liquitex and Rembrandt paints
and in the Lascaux green, and poly(2-ethylhexyl/methyl
methacrylate), p(2-EHA/MMA) copolymer in all the
Evaluation of lightfastness declarations of acrylic paints
Winsor & Newton and Schmincke samples and in the
Lascaux blue and red. The presence of a polyethoxylated
surfactant was detected in all acrylic emulsions by FTIR–
ATR, and in all the Liquitex specimens and in the
Schmincke green paint by plotting the single ion mass
profile of the marker ion fragment of octylphenol in the
thermal desorption pyrograms acquired with the double-
shot technique. Different types of extender were detected
by FTIR–ATR, for example kaolinite in the blue Liquitex,
Rembrandt, Lascaux, and Schmincke paints, and in all the
Lukas specimens, calcite in the Rembrandt red and green,
the Lascaux paints, and in the Lukas blue paint, barium
sulfate in all the Lukas samples, in the Schmincke green,
and in the Winsor & Newton red paints, and talc in the
Schmincke red paint.
After UV exposure, the results from chemical analysis of
the degradation products from the aged paints were
compared with the lightfastness declarations of the paints.
The results for the colours clearly showed that the change
induced by the UV exposure was not always correlated with
the lightfastness declarations on the paint tubes. For
instance, changes in the Py–GC/MS and FTIR–ATR
analyses were not observed for Lascaux blue (***,
lightfast), with quite a moderate lightfastness indication,
and it was one of the two most stable samples for colour
results in comparison with the other paints. In contrast, both
analytical techniques revealed that Lukas blue (***,
lightfast), with the same lightfastness specification, changed
most after UV ageing.
The thermal desorption step in the Py–GC/MS
experiments enabled detection of new volatile com-
pounds or new products, probably formed during the
photo-oxidative processes. FTIR–ATR, also, revealed
newly formed products including unspecific aldehydes,
lactones, and acidic oxidation products. An increase in
the brightness of the Lukas blue surfaces was noticed
after UV exposure and was also confirmed by colour
measurements.
Although the green acrylic paints generally seemed to be
more stable then the blue paints, analogous with the blue
samples, the effect of UV exposure could not always be
correlated with the lightfastness declarations. For example,
Lascaux green (**, limited lightfast) paint did not signif-
icantly change according to Py–GC/MS and FTIR–ATR,
and the colour measurement results indicated it was one of
the most stable paint materials. Lukas green (***, lightfast)
paint was most sensitive to UV; this was consistent with the
Py–GC/MS thermal desorption of the double-shot results,
which revealed the formation of some oxidation products.
By use of FTIR–ATR and colour measurements the
formation of a γ-lactone structure or open chain anhydrides
was observed, with substantial shifts of the a* and b*
coordinates.
1583
For the red paints, no significant differences were
revealed by Py–GC/MS and colour measurements,
although for the Liquitex red samples labelled with high
lightfastness (I, excellent) FTIR–ATR revealed a decrease
of the surfactant complemented by the formation of new,
unspecified, aldehydes, lactones, and acidic oxidation
products.
The Py–GC/MS and FTIR–ATR results generally indi-
cated that the UV resistance of the blue acrylic paints was
lower than that of the green and red colours. In addition,
this study clearly showed the advantage of the Py–GC/MS
double-shot technique in enabling detection of volatile
compounds after UV exposure, otherwise unnoticed with
the single-shot technique, which complemented the FTIR–
ATR data from the aged samples.
Acknowledgements This work was funded by Regione Sardegna
(Italy), “Programma Master and Back anno 2009” Alta Formazione
and the Austrian Science Fund, project no. L699-N17. We thank Oscar
Chiantore (Department of I.P.M. Chemistry and Nanostructured
Interfaces and Surfaces-Centre of Excellence, University of Torino,
Italy) for fruitful discussion and valuable cooperation on ageing
studies of acrylic materials. We also thank Rebecca Ploeger (National
Gallery of Art, Washington, DC, USA) for openly sharing her
knowledge and for helping with the English corrections. Moreover,
we are grateful to Antonia Cecini (Faculty of Chemistry, University of
Pavia, Italy) for carrying out the FTIR–ATR and colour-measurement
analyses.
References
1. Learner T (2004) Analysis of modern paints. The Getty
Conservation Institute, Los Angeles
2. Scalarone D, Chiantore O (2004) J Sep Sci 27:263–274
3. Pintus V, Schreiner M (2011) Anal Bioanal Chem 399:2961–2976
4. Sonoda N, Rioux JP (1990) Studies Conserv 35:189–204
5. Sonoda N, Rioux JP, Duval AR (1993) Studies Conserv 38:99–
127
6. Chiantore O, Scalarone D, Learner T (2003) Int J Polym Anal Ch
8:67–82
7. Jones FN, Mao W, Ziemer PD, Xiao F, Hayes J, Golden M (2004)
Prog Org Coat 52:9–20
8. Learner T (2000) The Conservator 24:96–103
9. Boon JJ, Learner T (2002) J Anal Appl Pyrol 64:327–344
10. Stringari C, Pratt E (1991) The identification and characterization
of acrylic emulsion paint media. In Saving the Twentieth Century,
Ottawa, Canada, pp 411–440
11. Learner T (1995) ‘The analysis of synthetic resins found in
twentieth-century paint media’ in Pre-prints, Resins: Ancient and
Modern. Scottish Society for Conservation and Restoration,
Edinburgh, pp 76–84
12. Learner T (2007) In: Learner T, Smithen P, Krueger JW, Schilling
MR (eds) Modern paints uncovered. The Getty Conservation
Institute, Los Angeles
13. Ormsby B, Kampasakali E, Miliani C, Learner T (2009) e-PS
6:186–195
14. Ormsby B, Learner T, Foster G, Druzik J, Schilling M (2007) In:
Learner T, Smithen P, Krueger JW, Schilling MR (eds) Modern
paints uncovered. The Getty Conservation Institute, Los Angeles
15. Hoogland FG, Boon JJ (2009) Int J Mass Spectrom 284:66–71
1584
16. Hoogland FG, Boon JJ (2009) Int J Mass Spectrom 284:72–
80
17. Dickson T (1988) In: Lewis PA (ed) Pigment handbook, vol 1,
2nd edn. New York, Wiley
18. Liquitex Artist Materials (2011). http://www.liquitex.com/AboutUs/.
Accessed 10 May 2011
19. Schmincke Acrylfarben (2011). http://www.schmincke.de/.
Accessed 10 May 2011
20. Lascaux Colours & Restauro (2011). http://lascaux.ch/de/index.
php. Accessed 10 May 2011
21. Lukas Künstlerfarben – seit 1862 (2011). http://www.lukas.eu.
Accessed 10 May 2011
22. Winsor & Newton – The World’s Finest Artists’ Materials (2011)
http://www.winsornewton.com/ Accessed 10 May 2011
23. Learner T, Chiantore O, Scalarone D (2002) “Ageing studies on
acrylic emulsion paints”, Preprints ICOM Committee for Conser-
vation 13th Triennial Meeting. James & James (Science Publish-
ers), Rio de Janeiro, pp 911–919
24. Whitmore PM, Colaluca VG (1995) Studies Conserv 40:51–64
25. Melo MJ, Bracci S, Camaiti M, Chiantore O, Piacenti F (1999)
Polym Degrad Stabil 66:23–30
26. Scalarone D, Chiantore O, Learner T (2005) “Ageing studies
of acrylic emulsion paints. Part II. Comparing formulations
V. Pintus et al.
with poly(EA-co-MMA) and poly(nBA-co-MMA) binders
”Preprints ICOM Committee for Conservation 14th Triennial
Meeting. James & James/Earthscan, The Hague, pp 350–358
27. Chiantore O, Lazzari M (2001) Polymer 42:17–27
28. Chiantore O, Trossarelli L, Lazzari M (2000) Polymer 41:1657–
1668
29. Doménech-Carbó MT, Silva MF, Aura-Castro E, Fuster-López L,
Kröner S, Martínez-Bazán ML, Más-Barberá X, Mecklenburg MF,
Osete-Cortina L, Doménech A, Gimeno-Adelantado JV, Yusá-
Marco DJ (2011) Anal Bioanal Chem 399:3155–3304
30. ASTM International (2011) D5383 – 02 (Reapproved 2010)
31. ASTM International (2011) D5398 – 97 (Reapproved 2010)
32. Hellgren AC, Weissenborn P, Holmberg K (1999) Prog Org Coat
35:79–87
33. Vahur S, Teearu A, Leito I (2010) Spectrochim Acta A 75:1061–
1072
34. Feller-Johnston R (2001) Color science in the examination of
museum objects nondestructive procedures. The Getty Conserva-
tion Institute, Los Angeles
35. Allen NS, Parker MJ, Regan CJ, McIntyre RB, Dunk WAE (1995)
Polym Degrad Stab 47:117–127
36. Nellamy LJ (1975) The infrared spectra of complex molecules.
Chapman and Hall, London