Anal Bioanal Chem (2011) 399:2961–2976
DOI 10.1007/s00216-010-4357-5
ORIGINAL PAPER
Characterization and identification of acrylic binding
media: influence of UV light on the ageing process
Valentina Pintus & Manfred Schreiner
Received: 3 August 2010 / Revised: 12 October 2010 / Accepted: 18 October 2010 / Published online: 3 November 2010
# Springer-Verlag 2010
Abstract This study characterizes and identifies two
different acrylic binding media such as Plextol® D498
and Primal® AC33, which are widely used in modern and
contemporary art. In order to investigate their fast photo-
oxidative deterioration when exposed to ultraviolet (UV)
light, ageing studies on these materials were carried out.
For this purpose, pure synthetic materials but also mixed
with different inorganic pigments were identified and
characterized before and after UV exposure by means of
pyrolysis-gas chromatography/mass spectrometry (Py-GC/
MS). Particular attention was paid to the comparison of two
different analytical methods: (1) single-shot method based
on a pyrolysis for the analysis of polymers and (2) double-
shot method, which allows a unique combination of thermal
desorption for the analysis of volatile compounds and
pyrolysis of the polymers themselves. These analyses
have been complemented by Fourier transform infrared
spectroscopy-attenuated total reflectance (FTIR-ATR)
studies. The comparison of the results obtained from
unaged samples and UV-aged clearly showed material
alterations as well as the formation of new products, which
were recorded by FTIR-ATR. Generally, these changes
Published in the special issue Analytical Chemistry for Cultural
Heritage with Guest Editors Rocco Mazzeo, Silvia Prati, and Aldo
Roda.
V. Pintus : M. Schreiner
Institute of Chemical Technologies and Analytics,
Analytical Chemistry Division, Vienna University of Technology,
Getreidemarkt 9/161,
1060 Vienna, Austria
V. Pintus (*) : M. Schreiner
Institute of Science and Technology in Art, Academy of Fine Arts,
Schillerplatz 3,
1010 Vienna, Austria
e-mail: v.pintus@akbild.ac.at
were more pronounced when the acrylic binding media
were mixed with pigments. The double-shot technique of
Py-GC/MS additionally allowed the detection of the phenolic
antioxidant in unaged Plextol® D498, but no oxidation
products could be identified by Py-GC/MS in all samples.
Keywords Py-GC/MS . FTIR-ATR . Double-shot
technique . Acrylic polymer . Paint materials . UV ageing
Introduction
Acrylic materials have been used widely in the artistic field
as well as in conservation and restoration since the late
1950s [1]. Based on ester of acrylic and methacrylic acids,
acrylics are distinguished as acrylic solutions and as acrylic
emulsions (waterborne dispersions), which are generally
more used by different artists than acrylic solutions because
of their insolubility in water when they are dry, for their
easy application in many layers, and for safety and
environmental reasons.
The first acrylic emulsion paint was PRIMAL AC33,
introduced by Rohm and Haas in 1953 [2]. Generally called
“latex” (dispersion of acrylic polymers in water), acrylic
emulsions are characterized by four basic components:
water, monomer, initiator, and surfactant. The latter is
composed of a hydrophilic portion, oriented into the
aqueous phase, and a hydrophobic portion, oriented into a
monomer droplet. The addition of a surface active agent
(surfactant) is essential for the lowering of the interfacial
tension between the monomer and water. They are
generally present in low concentration and they can be
anionic (e.g., sodium lauryl sulfate or dodecylbenzene
sulfonate), cationic (usually based on quaternary ammonium
compounds), and nonionic (e.g., alkyl phenol ethoxylates).
2962
Nonionic surfactants based on polyethoxylates are widely
used and more stable than natural colloid stabilizers because
their aqueous solutions are not subject to biodegradation by
microorganisms [3]. A specific study focused on the
characterization of poly(ethylene glycol) (PEG) compounds
in artists' acrylic emulsion paints from different paint
manufacturers have been carried out by Hoogland and Boon
[4]. The analysis included data from matrix-assisted laser
desorption/ionization mass spectrometry (MALDI-MS) and
nano-electrospray ionization mass spectrometry (nano-
ESI_MS(MS)). These techniques facilitated the analysis of
the molar mass distribution and end-groups of the PEGs,
which were found in the water extracts of pigmented and
unpigmented acrylic emulsion paint film, paint samples from
a palette, and several small painting samples [4].
Through the time, the chemical and physical properties
of the acrylic emulsions have been improved using several
chemically different additives. Depending on their type,
additives are able to modify color, to give resistance to heat
degradation, to improve the performance, and also to
increase resistance to light degradation [5]. The pigments
can influence the chemical stability of the acrylics. They
themselves can also be considered as additives. Organic
pigments tend to decrease the durability in comparison to
the inorganic. Titanium dioxide represents the most studied
pigment [6, 7]. Spathis et al. [6] studied the photo-
degradation of a series of Paraloid B72 films containing
titanium dioxide (TiO2) pigments. For this purpose, two
crystallographic different kinds of TiO2, anatase and
anatase/rutile mixtures, were used in different concentra-
tion. The results obtained by Fourier transform infrared
spectroscopy (FTIR), gel permeation chromatography, and
solubility measurements demonstrated that the presence of
anatase pigment significantly improved the photostability
of Paraloid films. In contrast, it has also been reported that
anatase can form radicals and may degrade the polymers
due to its high reactivity to ultraviolet (UV) radiation [8].
More studies concerning the influence of inorganic pig-
ments on acrylic emulsions seem desirable.
Several studies on the identification and characterization
of pigmented and unpigmented acrylic emulsions have been
carried out [3, 9–17]. One of the most detailed analytical
studies on synthetic paints is presented by Learner [18].
Py-GC/MS analytical technique allowed the identification
of each synthetic polymer class showing a characteristic
pyrogram. The main limitation of the technique was the
inability to carry out quantitative analysis on any of the
copolymers or mixtures of media, due to the quite common
fragmentation reactions on pyrolysis. Another analytical
method suitable for the identification of the compound class
is FTIR [19]. This technique is useful to fingerprint many
synthetic polymer systems, but it does not give information
about small differences of the chemical structures of the
V. Pintus, M. Schreiner
monomeric units in a polymer or about the molecular
weight distribution and end groups [15].
Due to their good pictorial properties, acrylic emulsion
materials have been widely used as binding media for
paints and even for artworks exposed to outdoor conditions.
This means that different weathering parameters such as
UV light, temperature, and humidity have to be considered
in order to develop a good protocol for ageing studies. In
outdoor environments, UV light plays an important role
especially its wavelengths that normally cannot pass
through commercial window glass. Usually, that UV range
is not considered for indoor work of art, e.g., in a museum.
The UV light is divided into different wavelength
regions such as UV-A (400 to 315 nm, near UV), which
is usually considered harmless to acryls, UV-B (315 to
280 nm, middle UV), which may cause discoloration,
cracks, and other damages on acrylic materials, and finally
UV-C (280 to 100 nm, far UV), which can cause chain
scissions and/or cross-linking of the chemical structure of
the polymers; however, UV-C is completely absorbed by
the atmosphere.
Over the past 20 years, the effects of photooxidation
reactions due to UV light have been studied in detail [1, 20,
21]. For this purpose, different sources of UV light were
applied such as fluorescent [1, 20, 22] or mercury high-
pressure lamps [21]. Scalarone et al. [22] demonstrated that
different two types of artists' acrylic emulsion paints have a
high stability to photooxidation using fluorescent lamps and
UV filters to remove the radiation below 400 nm. However,
no oxidation products were detected by Py-GC/MS and
infrared spectroscopy. Additionally, color measurements
indicated a high resistance to yellowing, and a decreased
solubility of all p(nBA/MMA) copolymer paint samples in
comparison with p(EA/MMA) copolymer paint samples
was determined.
Chiantore et al. [23] used a Xenon light source filtered
for λ<295 nm for acrylic polymers characterized by long
ester groups such as n-butyl groups and detected a fast and
extensive cross-linking in combination with some fragmen-
tation, due to the favored oxidation on the tertiary carbon of
the butyl group. When the alkyl side groups are short, the
chain scissions prevail over the cross-linking reactions [24].
In addition, some attentions have been paid to the
competition between the chain scission reactions and the
cross-linking reactions during the photooxidative degrada-
tion. This is mainly due to the glass temperature Tg of
the polymer. Polymer chains above their Tgs (surface
glass temperature transition) would preferentially undergo
cross-linking [25].
In contrast to these studies, the influence of UV-B light
on the stability/degradation of materials in artworks
presented under outdoor conditions has been investigated
rarely. Furthermore, just a few systematic investigations on
UV ageing studies on acrylic binding media 2963

the formation of volatile compounds, which can be formed
during photooxidative reactions and/or any changes by
means of Py-GC/MS, especially in the double-shot mode,
have been described in the literature so far [5].
This technique has been considered as a useful and
powerful technique for the identification and characteriza-
tion of volatile compounds, polymeric materials, and
additives [5]. One of the big advantages of the double-
shot technique is that no additional sample is needed. With
one specimen, two analytical analyses can be carried out:
thermal desorption for the analysis of volatile compounds
and pyrolysis for the polymer itself.
The aim of this work is the identification and
characterization of acrylic emulsions used as binding
media in contemporary work of arts and to understand
their chemical reactions during UV exposure. Therefore,
pure acrylic compounds as well as mixtures with
inorganic pigments were tested in order to study any kind
of interactions between the color materials and the binding
medium. The Py-GC/MS investigations were comple-
mented by applying FTIR-attenuated total reflectance
(ATR) to the mock-ups in a nondestructive manner, which
means that no sample material had to be gained from the
specimen.
Experimental
Sample preparation
Approximately 60 mg of pure acrylic binding media such
as Primal® AC33 and Plextol® D498 were cast on glass
plates, which produced a dried film thickness in a range of
10–20 μm. Additionally, different mock-ups of pure
Primal® AC33 and Plextol® D498 mixed with inorganic
pigments such as titanium white (rutile and anatase),
cadmium red, cadmium yellow, hydrated chrome oxide,
ultramarine blue dark, raw umber Cyprus, and ivory black
(Table 1) in a mixing ratio of about 3:1 were prepared on
glass plates. The film thickness of these dried paint mixed
samples was approximately in a range of 30–40 μm. In
total, 12 identical specimens for each pure acrylic binding

Table 1 List of investigated mock-ups and their chemical and technical properties

Mock-ups Color Pigment classical Chemical composition Color index: Constitution number
name generic name of pigment

Primal® AC33+titanium white White Titanium white rutile p(EA/MMA)+TiO2 PW6 69

(rutile)
Primal® AC33+titanium White Titanium white anatasium p(EA/MMA)+TiO2 PW6 54
white (anatasium)
Primal® AC33+cadmium Red Cadmium red p(EA/MMA)+CdS, xCdSe PR 108 21120
red No. 1, light
Primal® AC33+cadmium Yellow Cadmium yellow p(EA/MMA)+CdS PY 37 21060
yellow No. 9 dark
Primal® AC33+hydrated Green Viridian p(EA/MMA)+Cr2O3 PG 18 44250
chrome oxide
Primal® AC33+ultramarine Blue Ultramarine blue p(EA/MMA)+ PB 29 45010
blue dark Na8Al6Si6O24.Sx
Primal® AC33+raw umber Brown Raw umber Cyprus p(EA/MMA)+ PBr 8 40610
Cyprus Fe2O3.H2O, MnO2
Primal® AC33+ivory black Black Bone (ivory) black p(EA/MMA)+C, PBk 9 47150
Ca3(PO4)2, CaCO3
Plextol® D498+titanium White Titanium white rutile p(nBA/MMA)+TiO2 PW6 69
white (rutile)
Plextol® D498+titanium White Titanium white anatasium p(nBA/MMA)+TiO2 PW6 54
white (anatasium)
Plextol® D498+cadmium Red Cadmium red p(nBA/MMA)+CdS, xCdSe PR 108 21120
red No. 1, light
Plextol® D498+cadmium Yellow Cadmium yellow p(nBA/MMA)+CdS PY 37 21060
yellow No. 9 dark
Plextol® D498+hydrated Green Viridian p(nBA/MMA)+Cr2O3 PG 18 44250
chrome oxide
Plextol® D498+ultramarine Blue Ultramarine blue p(nBA/MMA)+ PB 29 45010
blue dark Na8Al6Si6O24.Sx
Plextol® D498+raw umber Brown Raw umber Cyprus p(nBA/MMA)+Fe2O3. PBr 8 40610
Cyprus H2O, MnO2
Plextol® D498+ivory black Black Bone (ivory) black p(nBA/MMA)+C, PBk 9 47150
Ca3(PO4)2, CaCO3
2964
medium and three for each pigment mixed with an acrylic
emulsion were made, in order to obtain sufficient samples
for the tests in the UV chamber. After drying for 24 h at
room temperature, all glass plates were arranged in the UV
chamber, except standard samples for the unaged compo-
sition. All acrylic emulsions binding media and inorganic
pigments are products of KREMER (Kremer Pigmente
Gmbh & Co. KG, Germany) except the white pigments,
which are part of the material collection of the ISTA
(Institute for Science and Technology in Art) at the
Academy of Fine Arts in Vienna.
UV exposure
UV exposure of the samples was carried out in a UV
chamber UVACUBE SOL 2/400F produced by Dr.
Hönle GmbH UV-Technology, Germany. The radiation
source of UV light was supplied by a 910-W/m2 Xenon
arc solar simulator with an incorporated H2 filter, which
provides radiation with wavelengths between 295 and
800 nm. The chamber temperature was 48.8 °C; the
relative humidity (RH) varied between 30% and 35%,
depending on the RH in the ambient atmosphere.
Unfortunately, no control of the RH is possible in the
UV exposure chamber used. Samples were aged for 31
and 83 days, respectively.
Pyrolysis gas chromatography/mass spectrometry
(PY-GC/MS)
For the identification and characterization of the samples
before and after UV exposure, analyses with pyrolysis gas
chromatography/mass spectrometry (Py-GC/MS) were car-
ried out. Particular attention was paid to the comparison of
two different analytical methods: (1) single-shot method
based on pyrolysis for the analysis of polymers and (2)
double-shot method, which allows the combination of
thermal desorption for the analysis of volatile compounds
and pyrolysis of the polymers themselves. In order to
perform the thermal desorption of the volatile compounds,
the sample is dropped down in a small cup by the
Fig. 1 Schematic heating curve
of the double-shot technique
for Py-GC/MS 600˚C
300˚C
50˚C
Thermal Desorption
V. Pintus, M. Schreiner
autosampler into the furnace of the pyrolyzer and heated
under the desired temperature conditions (e.g., from 50 °C
to 300 °C in approximately 16 min) as it is shown in Fig. 1.
When the thermal desorption program is finished, the
sample cup containing the remaining fraction is pulled up
from the heated zone, while the volatile organic compounds
produced from the thermal desorption are analyzed by the
GC/MS. Meanwhile, the furnace is cooled down to
approximately 60 °C (autocooling) and then heated to the
pyrolysis temperature conditions (e.g., 600 °C). As soon as
the GC/MS finishes to chromatographically separate and
detect the volatile compounds, the sample cup is dropped
down for a second time into the pyrolyzer furnace in order
to perform flash pyrolysis, and the sample material is
analyzed by the GC/MS.
For this investigation, Py-GC/MS analyses were per-
formed with a PY AOC-20i (Frontier Lab, Japan) combined
with a GCMS-QP2010 Plus (Shimadzu, Japan) equipped
with a capillary column SLB-5ms SUPELCO, USA
(30 m×0.25 mm×0.25 μm) using bonded and highly
cross-linked 5% diphenyl/95% methyl siloxane.
The GC column temperature conditions were as follows:
initial temperature 40 °C, hold for 5 min, and afterwards
increased by 10 °C/min to 292 °C. The helium gas flow
was set at 1 mL/min, 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; the temperature of the pyrolysis interface
and the injector was set at 250 °C.
The double-shot parameters were as follows: for the
thermal desorption, the temperature was set at 50 °C, held
for 2 min, and increased by 20 °C/min to 300 °C and held
there for 2 min. After cooling (autocooling to approximate-
ly 60 °C), the pyrolysis was carried out at 600 °C and held
for 1 min.
Between 80 and 300 μg of the samples were scraped
from the mock-ups with a scalpel and put in a sample cup
(ECO-CUP Frontier Lab, Japan) in order to provide the
analysis through the pyrolyzer. NIST 05 and NIST 05s
Library of Mass Spectra were used for identifying the
compounds.
Pyrolyzer furnace temp.
Sample temp.
Autocooling
GC Analysis Flash Pyrolysis Time
UV ageing studies on acrylic binding media 2965

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 triglicine sulfate detector
(DTGS) and with a diamond crystal. Spectra were acquired
in a spectral range between 4,000 and 370 cm−1 performing
64 scans at 4 cm−1 resolution. The resulting spectra were
collected and evaluated with the spectrum software OPUS®
of Bruker Optics.
Results and discussion
Unaged samples
Pure acrylic binding media: Py-GC/MS results
The pure acrylic binding medium Primal® AC33 was
identified and characterized as a co-emulsion of poly(ethyl
acrylate/methyl methacrylate), p(EA/MMA). This product
is usually used as adhesive, consolidant [26], as well as
binding medium in the field of conservation-restoration but
also by artists. Nowadays, it is out of production by
Kremer, but other companies, which provide also materials
for art and restoration, produce similar products as
Rhoplex® AC 33 (Rohm and Haas, Germany) and Acrylic
33 EMULSIONE ACRILICA (Bresciani, Italy), which are
widely used.
It is well known that under pyrolysis condition, p(EA/
MMA) binding media decompose to the respective mono-
mers as well as to dimers and trimers in lower amounts [9,
11, 18]. As described by Learner [18], due to the presence
of tertiary hydrogen atoms on the polymer chain, acrylates
are prone to the abstraction of the hydrogen with a
subsequent production of free radicals along the polymer
chain. This permits the production of various oligomers.
The identification of Primal® AC33 as p(EA/MMA) is
challenging due to the same molecular weight of both
monomers. For instance, the assignment of the EA-EA-
MMA trimers reported in the literature is based on the
expected retention time, due to their similar mass spectra
[11].
In Fig. 2 (pyrogram a), the most intense peak is related
to ethyl acrylate (EA) at RT 4.1 min with a molecular ion at
m/z=55 from the loss of an ethoxy side group. At similar
retention times (RT 4.4 min), the methyl-methacrylate

Fig. 2 Overall pyrograms of f)

Primal® AC 33 p(EA/MMA). a
Unaged sample analyzed in IV
single-shot mode (SS) and (b)
I
unaged sample analyzed in II III
double-shot mode: thermal e)
desorption and (c) pyrolysis. d
Aged sample (83 days) analyzed
in single-shot mode and (e) aged
d)
sample analyzed in double-shot
mode: thermal desorption and
(f) pyrolysis. Peaks labeled 1
and 2 correspond to phtalic acid,
Relative intensity

di-(1-hexen-5-yl)ester, and
phtalic acid, monobutyl ester,
respectively. Peaks labeled I
(octyl ether m/z=57, 70, 112,
and 129), II (octyl ether
m/z=57,70, 112, and 127), III
(di-n-octyl phthalate m/z=57, c)
71, 113, 149, 207, and 279), 2
1
and IV (squalene m/z=55, 69,
b)
MMA
EA

95, and 121) probably from

air or contaminations
trimers
sesquimer-dimer
EMA

a)
0 10 20 30 40
Retention time (min)
2966
(MMA) monomer was detected with the characteristic m/z=
69. A less intense peak of EMA with m/z=69 was recorded
at RT 6.6 min. In a previous study [27], this peak suggested
that two analyzed acrylic emulsions such as Plextol® B500
and Primal® AC33 could be terpolymers of p(EA-MMA-
EMA). As discussed by Learner [14], the EMA presence
cannot be ascribed to this terpolymer species because they
are produced on pyrolysis of the pEA homopolymers. The
two peaks of EA and MMA indicate a co-emulsion of EA/
MMA polymer. In addition, four peaks corresponding to
EA-MMA sesquimer (one and a half monomer unit
molecule) at RT 20.5 min (m/z=55, 101, 128, and 157),
EA-MMA dimer at RT 21.3 min (m/z=67, 95, 140, and
168), EA sesquimer at RT 21.4 min (m/z=55, 87, 143, and
162), and EA dimer at RT 22.6 min (m/z=53, 98, 126, 154,
and 200) were identified (Fig. 2, pyrogram a). EA dimer
corresponds to the largest peak in this group, while the EA-
MMA sesquimer and dimer are the less intense one. It was
also possible to observe two peaks of EA-EA-MMA trimer
(m/z=55, 93, 139, 166, 200, 255, 269 and m/z=55, 93, 121,
167, 200, 255, 269) at RT 31.3 min and at RT 33.0 min and
Fig. 3 Recognition of an octyl
phenyl polyethoxy ethanol
surfactant in Primal® AC33,
p(EA/MMA) acrylic emulsion:
a total ion chromatogram
(×10,000,000) of the unaged
sample analyzed in single-shot
mode and (b) single ion mass
profile at m/z 135, a marker ion
fragment of octyl phenol. c Total
ion chromatogram
(×10,000,000) of the sample
analyzed in single-shot mode
after 83 days of UV ageing and
(d) single ion mass profile at
m/z 135, a marker ion
Relative intensity
fragment of octyl phenol
0 10
V. Pintus, M. Schreiner
a peak of EA trimer (m/z=79, 106, 134, 181, 208, and 255)
at RT 32.7 min (Fig. 2, pyrogram a). The identification of
these compounds is in accord with several other case
studies [3, 18], and it was possible to detect them in the
single-shot mode.
The double-shot mode, more precisely with the thermal
desorption shown in Fig. 2 (pyrogram b), allowed the
identification of two chemical fragments such as phtalic
acid, di–(1–hexen–5–yl)ester (m/z=65, 93, and 149) at RT
28.2 min (indicated with the peak labeled 1) and phtalic
acid, monobutyl ester (m/z=56, 93, 149, and 160) at RT
34.8 min (indicated with the peak labeled 2), which may
indicate the presence of a phthalate–ester-based plasticizer,
which are additives mainly incorporated into polymers by
blending and commonly used in thermoplastic polymers in
order to increase their flexibility, workability, or extensibility
[28]. However, their detection is ambiguous, as any peak
related to the phthalate plasticizer was detected in the
single-shot mode at higher temperature. Due to their very
low concentration and high volatility, they may also derive
from air pollutants or contamination in the laboratory.
d)
m/z 135
TIC
c)
m/z 135 b)
TIC
a)
20 30 40
Retention time (min)
UV ageing studies on acrylic binding media 2967

Additionally, it was possible to detect some marker
peaks of a nonionic surfactant such as octyl phenyl
polyethoxy ethanol, which is commonly present in the
recent paint formulations. Generally, they are in small
concentrations, and its marker peaks might be partially or
totally overlaid by other components. Due to the fact that
the presence of pyrolysis fragments of the nonionic
surfactant was not evident from the total ion chromatogram,
by plotting the corresponding single ion mass profiles at
m/z=135, the octyl phenol (m/z=135, 206) was detected
(Fig. 3, pyrogram b). This is a marker compound of
alkyraryl polythoxylates for the nonionic surfactant octyl
phenyl polyethoxy ethanol [3].
In contrast to these results, Plextol® D498 was
characterized as a co-emulsion of poly(butyl acrylate/
methyl methacrylate), p(nBA/MMA). Nowadays, most of
the artists' acrylic emulsion paints are based on p(nBA/
MMA) copolymers [29], which show superior hydropho-
bicity in comparison with p(EA/MMA). Unlike p(EA/
MMA), MMA and nBA have a different molecular weight,
and their oligomers can be easily distinguished by
identification of their mass spectra. The pyrogram of
Plextol® D498 in Fig. 4 (pyrogram a) depicted the most
intense peak of nBA (m/z=55, 73, 85, and 128) at RT
10.6 min, where the intense fragment peak at m/z=55 is
similar to EA. The production of n-butene and protonated
acrylic acid is indicated by the additional masses at
m/z=56 and 73, respectively. MMA peak (m/z=69 and
100) was also detected at RT 4.4 min. Another peak at RT
3.5 min was identified as n-butanol (m/z=56). Addition-
ally, a peak corresponding to nBMA (m/z=56, 69, and 87)
was detected at RT 13.3 min. As it was observed for
Primal® AC33 at higher retention times, several peaks
were recorded (Fig. 4, pyrogram a). The first group of four
peaks corresponds to the sesquimers and dimers. Under
electron impact ionization (EI) even if the molecular ions
are not detected, the sesquimers and dimers can be
recognized by characteristic fragment ions obtained by

Fig. 4 Overall pyrograms of

Plextol® D498 p(nBA/MMA).
a Unaged sample analyzed in
single-shot mode (SS) and (b) f)
unaged sample analyzed in
double-shot mode: thermal 1 3 5 e)
desorption and (c) pyrolysis. d
nBA

Aged sample (83 days) analyzed

in single-shot mode and (e) aged
sample analyzed in double-shot
mode: thermal desorption and
(f) pyrolysis. Peaks: (1) phthalic d)
anhydride (m/z=76, 104, and
148), (3) diethyl phthalate
(m/z=65, 93, 149, and 177), (5)
phthalic acid, butyl undecyl
ester (m/z=57, 104, 121, and
Relative intensity

149), and (2) phenol,3,5-

bis(1,1-dimethylethyl)
(m/z=57, 91, 135, 163, 191,
and 220), (4) phenol,2-(1,1-
dimethylethyl)-4-(1,1,3,
3-tetramethylbutyl) (m/z=57, c)
91, 147, 175, 191, and 262)

1 3 4 b)
2 5
MMA

sesquimer-dimer

trimers
n-butanol

nBMA

a)

0 10 20 30 40
Retention time (min)
2968
scission of a methoxy or butoxy group to give [M-31]+
and [M-73]+ cations. Two peaks were related to nBA
sesquimer (m/z=57, 87, 115, 142, 171, and 189) and to
nBA dimer (m/z=57, 98, 127, and 183) at RT 29.5 min
and at RT 30.4 min, respectively. The other two peaks at
RT 24.9 min and at RT 25.5 min were identified as nBA-
MMA sesquimer (m/z=55, 73, 115, 143, and 185) and
nBA-MMA dimer (m/z=57, 67, 95, 112, 126, and 141).
The later group of four peaks corresponds to the trimers.
The most intense peak is the pure nBA trimer (m/z=57,
109, 134, 181, 208, 236, 282, and 311) at RT 40.9 min.
The other three peaks eluted at RT 37.0, 37.4, and
38.9 min are the nBA-nBA-MMA trimers (m/z=57, 93,
139, 195, 250, 283, 325; m/z=57, 93, 120, 167, 195, 250,
283, 325; and m/z=57, 93, 121, 167, 195, 228, 283, 296;
Fig. 4, pyrogram a).
Unlike Primal® AC33, the detection of the sesquimers,
dimers, and trimers is shown already during the thermal
desorption in the double-shot mode (Fig. 4, pyrogram b).
Due to the presence of the oligomers in the thermal
desorpted pyrogram, the unzipping effect of the polymer
seems to be less in comparison to the pyrolyzed pyrogram,
whereas at this higher temperature, the complete decompo-
sition of the polymer occurred with the production of
monomers.
Fig. 5 Recognition of an octyl
phenyl polyethoxy ethanol
surfactant in Plextol® D498,
p(nBA/MMA) acrylic emulsion.
a Total ion chromatogram
(×1,000,000) of the unaged
sample analyzed in double-shot
mode, thermal desorption, and
(b) single ion mass profile at
m/z 135, a marker ion fragment
of octyl phenol. c Total ion
chromatogram (×1,000,000)
of the sample analyzed in
double-shot mode after
Relative intensity
83 days of UV ageing,
thermal desorption, and
(d) single ion mass profile
at m/z 135, a marker ion
fragment of octyl phenol
0 10
V. Pintus, M. Schreiner
Furthermore, with the double-shot technique in the
thermal desorption mode, peaks were registered related to
the phthalic anhydride (m/z=76, 104, and 148) at RT
22.4 min, to the diethyl phthalate (m/z=65, 93, 149, and
177) at RT 28.2 min, and to phthalic acid, butyl undecyl
ester (m/z=57, 104, 121, and 149) at RT 34.9 min, which
are commonly known to be related to a phthalate-based
plasticizer. They are indicated in Fig. 4 (pyrogram b) with
the peak numbers 1, 3, and 5, respectively. As for Primal®
AC33, they possibly derive from sample contamination or
from air pollutants, since no peaks related to the phthalic
plasticizer are recorded in the pyrolysis. In Fig. 4 (pyrogram
b), other two peaks labeled as numbers 2 and 4 were
detected possibly related to an antioxidant: phenol,3,5-bis
(1,1-dimethylethyl) (m/z=57, 91, 135, 163, 191, and 220) at
RT 26.6 min and phenol, 2-(1,1-dimethylethyl)-4-(1,1,3,3-
tetramethylbutyl) (m/z=57, 91, 147, 175, 191, and 262).
Similar to Primal® AC33, the octyl phenol was detected
(Fig. 5, pyrogram b) by plotting the corresponding single
ion mass profiles at m/z=135. Due to its low intensity in the
pyrogram of the single-shot mode, it is only visible by
plotting the corresponding single ion mass profile in the
thermal desorption pyrogram, acquired with the double-shot
mode. In this case, the presence of m/z=135 marker ion
fragment was clearly acquired (Fig. 5, pyrogram b).
d)
m/z 135
c)
TIC
m/z 135 b)
a)
TIC
20 30 40
Retention time (min)
UV ageing studies on acrylic binding media 2969

Pure acrylic binding media: FTIR-ATR results C–H bending (1,300–1,500 cm−1): Plextol® D498 has
the most intense peak at 1,449 cm−1 and a smaller one
The FTIR-ATR results of the two acrylic emulsion binding at 1,386 cm−1 close to other two small peaks at 1,360
media are shown in Table 2 and summarized in the and 1,343 cm−1. Primal® AC33 has a double peak at
following regions: 1,466 and 1,451 cm−1 and a less intense one at
1,381 cm−1. Additionally, other two peaks were
C–H stretching (2,800–3,100 cm−1): Primal® AC33 detected at 1,360 and 1,343 cm−1, similar but with a
showed the main C–H stretching frequencies at higher intensity than for Plextol® D498.
2,888 cm−1 complemented by two smaller peaks at C–O stretching C–C skeletal vibrations (900–1,250 cm−1):
2,949 and 2,741 cm−1. In contrast, the spectrum of In this frequency region, a double peak at 1,159 and
Plextol® D498 had two peaks at 2,955 and 2,929 cm−1 1,143 cm−1 was observed in the Plextol® D498 spectrum
and a smaller one at 2,874 cm−1. with another less intense peak at 1,236 cm−1. Primal®
C=O stretching (1,700–1,750 cm−1): In both spectra AC33 showed the most intense one at 1,109 cm−1 and
for Primal® AC33 and Plextol® D498, the carbonyl other two intense peaks at 1,149 and 1,240 cm−1.
stretching absorption occurs at a similar wavelength, at
1,723 and at 1,726 cm−1, respectively. Additionally, polyethoxylated surfactant with the char-
acteristic absorption bands at 2,890, 1,455, 1,343, 1,296,
1,110, 945, and 842 cm−1 [22] was detected in the
Primal® AC33 and Plextol® D498 acrylic emulsions. Due
Table 2 ATR infrared absorptions of the investigated acrylic binding to the main absorption of the acrylic emulsion binding
media media, in the case of Primal® AC 33, the most visible
Bond type Primal® AC33 Plextol® D498
peaks corresponded to 2,890, 1,343, 1,110, and 963 cm−1.
p(EA/MMA) (cm−1) p(nBA/MMA) (cm−1) Unlike Primal® AC33, Plextol® D498 showed only two
peaks at 1,343 and 1,110 cm−1 characteristic for the
C–H rock 759 754 surfactant.
– 808
843 842 Acrylic binding media mixed with inorganic pigments:
C–C stretching – 944 Py-GC/MS and FTIR-ATR results
964 963
– 990 Mainly due to the presence of the inorganic compounds in
C–O stretching 1,021 1,022 the matrix, the Py-GC/MS results obtained from both
1,061 1,063 acrylic binding media mixed with inorganic pigments did
1,109 1,115 not show any differences in comparison with the pure
1,149 1,143 acrylic binding media described in “Pure acrylic binding
– 1,159 media: Py-GC/MS results” section. Also, the FTIR-ATR
1,240 1,236 spectra are the results of the spectra of the pure pigments
1,279 – and of the binding media themselves and will not be
C–H bending 1,343 1,343 discussed in detail here. Nevertheless, some of the pigments
1,360 1,361 used for preparing the mock-ups masked in some infrared
1,381 1,386 regions the detection of the binding media with their strong
– 1,436 shoulder infrared absorption. For instance, blue ultramarine, which is
1,451 1,449 a pigment composed of silicon, aluminum, sodium, sulfur,
1,466 – and oxygen, shows overlapping stretching bands for Si–O–
1,513 – Si and Si–O–Al between 1,150 and 950 cm−1. These bands
C=O stretching 1,723 1,726 interfered with the C–O/C–C skeletal vibrations (900–
C–H stretching – 2,852 shoulder 1,250 cm−1) regions of the acrylic binding media. More-
2,860 – over, these regions are masked by the ivory black pigment,
– 2,874 which is composed of amorphous carbon with calcium
2,888 – phosphate Ca3(PO4)2 and calcium carbonate CaCO3, with
– 2,931
an intense peak at 1,020 cm−1 of the phosphate groups. The
2,949 –
umber Cyprus pigment based on iron oxide Fe2O3 with
2,955
water manganese oxide MnO 2 has a band around
1,000 cm−1 of the iron oxides.
2970
Aged samples
Pure acrylic binding media: Py-GC/MS results
The comparison between the results obtained from unaged
and aged samples reveals that the effects of the photoox-
idative reactions could be determined only after 83 days of
UV exposure. The main difference between UV-aged and
unaged Primal® AC33 sample is the gradual reduction in
area of the main peaks, which is shown in Fig. 2 (pyro-
grams d and e). The most intense peak of EA in comparison
with the MMA peak decreased gradually after UV
exposure, whereas the MMA peak became the most intense
one. In addition, the dimers, sesquimers, and trimers peaks
diminished almost totally, which is mainly due to the
photodeterioration of the ethyl groups. Additionally,
another indication for a photooxidation process was shown
by the surfactant: plotting the corresponding single ion
mass profile at m/z=135 of octyl phenol detected in the
unaged sample in the pyrolysis pyrogram acquired with the
single-shot mode, no traces were found in the pyrogram of
the aged material (Fig. 3, pyrogram d). The only difference,
which could be noticed to the results obtained in the
double-shot mode, was the detection of the dimers, trimers,
and sesquimers peaks in the thermal desorption pyrogram,
which were not detected in the unaged material. The
photoageing processes have evidently changed the thermal
stability of the sample with a consequent production of
oligomers already during the thermal desorption and
almost no longer detectable in the pyrolysis. New peaks
clearly visible in the thermal desorption (Fig. 2, pyrogram
e) at RT 37.1 min (octyl ether m/z=57, 70, 112, and 129,
labeled I), at RT 40.0 min (octyl ether m/z=57, 70, 112, and
127, labeled II), as at RT 43.3 min (di-n-octyl phthalate
(x10,000)
1.0
57
a) 0.5
191
91 163
135
0.0
50 150 200
Relative intensity
26.50 26.75 27.00 27.25
Retention time (min)
Fig. 6 a, b Detail of the pyrograms of Plextol® D498 p(nBA/MMA).
a Unaged sample analyzed in single-shot mode (SS) and (b) aged
sample (83 days) analyzed in single-shot mode and (c) unaged sample
analyzed in double-short mode: thermal desorption and d pyrolysis.
V. Pintus, M. Schreiner
m/z=57, 71, 113, 149, 207, and 279, labeled III) and at
RT 46.8 min (squalene m/z=55, 69, 95, and 121, labeled
IV) are probably from the ambient atmosphere or other
contaminations.
Concerning Plextol® D498, the main difference between
the UV-aged and unaged sample is the total decrease of the
phenolic antioxidant peak (Fig. 6a, pyrogram c), which was
detected in the unaged sample by the double-shot mode.
These additives are generally considered having poor
photostability [30, 31]. Another product, which was
difficult to be detected in the aged pure and pigment-
mixed Plextol® D498 acrylic binding medium, was the
butyl group (Fig. 6b, pyrograms a and d), which is more
sensitive to photooxidation reactions compared to the
acrylic binding media with a lower structural unit, e.g.,
methyl or ethyl group [23]. When the ester side group is
short, chain scissions occur to a higher extent than cross-
linking reactions.
Furthermore, similar to Primal® AC33, it is possible to
see in Fig. 4 (pyrograms d and f) a strong reduction of the
areas of the dimers, sesquimers, and trimers peaks, which
might be due to the photooxidation of the butyl group.
These peaks were already detected in the thermal desorp-
tion pyrogram (Fig. 4, pyrogram e), but their areas are
reduced in comparison with the unaged sample. Another
difference between the unaged and aged samples related is
shown by the peak of nBA in Fig. 4 (pyrograms a, c, d, and
f). In pyrograms a and c, the peak of nBA is the most
intensive and especially more intense than the peak of
MMA. After 83 days of UV exposure, it became consid-
erably less intense.
Similar to Primal® AC33 by plotting the corresponding
single ion mass profile at m/z=135 of the previous detected
octyl phenol in the thermal desorption pyrogram, acquired
(x10,000)
1.0
56
b) 0.5
87
220 0.0
50 100
f) f)
e) e)
d) d)
c) c)
b) b)
a) a)
27.50 27.75 6.5 7.0 7.5 8.0 8.5
Retention time (min)
(e) Aged sample analyzed in double-shot mode: thermal desorption
and (f) pyrolysis. a Shows the mass spectra of the phenolic antioxidant
which can not be detected in the aged sample. b Shows the mass
spectra of the butyl ester which is not detected in the aged sample
UV ageing studies on acrylic binding media 2971

Fig. 7 FTIR-ATR spectra of 1725 1139

2.0
Plextol® D498 p(nBA/MMA)
mixed with cadmium red
before (a), after 31 days of UV
ageing (b), and 83 days of
UV ageing (c)

1.5
Absorbance Units
1233

1.0
983
1447 753
1385 841

0.5 2955 c)

2874 b)

a)
0.0

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1

with the double-shot mode, no traces were found anymore
(Fig. 5, pyrogram d).
Besides these differences, in both Primal® AC33 as well
as Plextol® D498, no formation of new peaks related to
new volatile compounds or new products, which could be
formed during the photooxidative process, could be
detected.
Pure acrylic binding media: FTIR-ATR results
The comparison of the spectra obtained from unaged and
aged Plextol® D498 as well as Primal® AC33 shows
differences mainly based on the progressive decrease of all
principle absorptions, which might be due to the loss of
volatile compounds. Especially the gradual reduction of the
absorption of the carbonyl group at 1,726 cm−1 can be
related to the loss of the butyl group of the Plextol® D498
and of the ethyl group related to the Primal® AC33.
Additionally, the broadening of the carbonyl band indicates
a progressive absorption (1) at 1,773 cm−1 corresponding
probably to the formation of a γ-lactone structure, which
absorbs at 1,780 cm−1 [21, 24, 32], or to the formation of
open chain anhydrides, which absorb at 1,800 cm−1 [33].
(2) Additionally, the frequency region between 1,600 and
1,710 cm−1 is of interest, which may be related to the
formation of unsaturated molecules with a C=C bond at

Fig. 8 FTIR-ATR spectra of 1723 1108

Primal® AC33 p(EA/MMA)
2.0

mixed with cadmium red

1153
before (a), after 31 days of
UV ageing (b), and 83 days
of UV ageing (c)
1.5
Absorbance Units

1019
1.0

1234
963
1342 850
2887 1381
1445 756
0.5

2950
2980
c)

b) a)
0.0

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1
2972 V. Pintus, M. Schreiner

Fig. 9 FTIR-ATR spectra of

2.0
Primal® AC33 p(EA/MMA)
mixed with rutile titanium white
before (a), after 31 days of 1109
UV ageing (b), and 83 days
of UV ageing (c)

1.5
1722

Absorbance Units
1148

1.0
2886 1240 1061
1341 1022
842
1381 963
2949 1444
2980

C
B
A
0.0

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1

1,652 cm−1, due to polymer chain scissions [21]. It might
be also a result from the formation of ketones absorbing at
1,710 cm−1 as a consequence of the reaction of oxygen
molecules with radicals and followed by ß-scission [34].
A gradual reduction of the absorption of the character-
istic peaks of PEG type surfactant was observed by both
acrylic emulsions after UV exposure. Especially after
83 days of UV ageing, the sharp peaks at 2,890, 1,343,
1,110, and 963 cm−1 totally decreased according to the Py-
GC/MS results, which also did not show any traces of the
surfactant found in unaged samples. These differences are
clearly visible also when they are mixed with pigments
(e.g., Fig. 7). Similar results have been reported in the
literature [22, 35].
Acrylic binding media mixed with inorganic pigments:
Py-GC/MS results
The acrylic binding media mixed with inorganic pigments did
not show significant changes after the UV exposure, apart
from a more pronounced decrease of all principal peaks and
formation of new small peaks with a characterization mass
m/z=59, 83, 99, 141, and 169 which were detected by the
thermal desorption. Unfortunately, it was not possible to

Fig. 10 FTIR-ATR spectra of

2.0

Plextol® D498 p(nBA/MMA)

mixed with blue ultramarine
before (a), after 31 days of 962
UV ageing (b), and 83 days
of UV ageing (c)
1.5

1727
Absorbance Units

1112
1144
1.0

651
688
582
1236
0.5

2955 1450
1385
2874
B C
A
0.0

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1
UV ageing studies on acrylic binding media 2973

Fig. 11 FTIR-ATR spectra of 1725

2.0
Plextol® D498 p(nBA/MMA)
mixed with umber Cyprus
before (a), after 31 days of
UV ageing (b), and 83 days
1142
of UV ageing (c) 1160

1.5
Absorbance Units
1.0
b)
c)
1449
0.5 1385
2955 841 a)
1063
2874
754
0.0

3500 3000 2500 2000 1500 1000 500

-1
Wavenumber cm

identify those peaks, which could be primarily registered for pigment mixed with Plextol® D498 as well as with Primal®
the samples with Plextol® D498 mixed with blue ultrama- AC33 before and after UV exposure showed some changes in
rine. It might be due to the presence of the blue pigment in the IR absorption similar to alterations recorded from the aged
the acrylic binding media, which influences its stability. pure acrylic binding media:

Acrylic binding media mixed with inorganic pigments:
FTIR-ATR results
Acrylic emulsions mixed with inorganic or organic pigments
can behave differently during UV exposure. Pigments might
affect the stability of the polymers as well as the properties of
the paint formulation and catalyzing photochemical reactions.
In our study, the comparison of the results obtained for each
Fig. 12 FTIR-ATR spectra of
2.0
(a) A gradual broadening in the region between 3,600 and
3,000 cm−1, which might be due to the formation of
associated hydroxyl groups, belonging to alcoholic
and/or hydroperoxidic structures [21].
(b) In general, the absorption of the carbonyl peak at
1,722 cm−1 decreased gradually after 31 and 83 days
of UV ageing. However, in the case of cadmium red
mixed with Plextol® D498 (Fig. 7), that change could
1722 1152 1111

Primal® AC33 p(EA/MMA)

mixed with cadmium yellow
before (a), after 31 days of UV
ageing (b), and 83 days of UV
ageing (c) 1018
1.5
Absorbance Units

1233
963
849
1.0

1379
1444 1343
755
2950
2980 2888

c)
0.5

b) a)
0.0

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1
2974 V. Pintus, M. Schreiner

Fig. 13 FTIR-ATR spectra of 1110

2.0
Primal® AC33 p(EA/MMA)
mixed with anatase titanium
white before (a), after 31 days of
UV ageing (b), and 83 days of
UV ageing (c)

1.5
1723 1149
b)

Absorbance Units
c)

1.0
1239 a)
1021
1342 843
1381 964
2889
0.5
1445
2950 752
2984
0.0

3500 3000 2500 2000 1500 1000 500

-1
Wavenumber cm

not be observed. This is probably due to the compen-
sation of the loss of ester groups with some new
oxidation products such as aldehyde groups absorbing
in the same region and formed by reaction of the
secondary macroradical with oxygen [24]. In contrast to
these results, Primal® AC33 mixed with cadmium red
(Fig. 8), as well as with the rutile titanium white
(Fig. 9), showed a higher absorption in this range.
(c) Significant for the photooxidative processes of the
samples is the progressive broadening of the carbonyl
band in the frequency regions between 1,830 and
1,730 cm−1 and between 1,710 and 1,600 cm−1. In the
case of Plextol® D498 mixed with blue ultramarine
(Fig. 10), the broadening in these regions is related to
the increase of γ-lactones [21, 24, 32, 33], and it is well
pronounced in comparison to the broadening of the
region of the ketones groups or open chain anhydrides.
Completely different results were obtained for Plextol®
D498 mixed with the umber Cyprus (Fig. 11). A higher
absorption in the region between 1,710 and 1,600 cm−1 could
be observed in comparison to the γ-lactone region (1,830–
1,700 cm−1). Similar results were obtained for the mixture of
cadmium yellow with Primal® AC33 (Fig. 12).
Additionally, acrylic media mixed with pigments showed a
total decrease in absorption of the bands of the nonionic

Fig. 14 FTIR-ATR spectra of 1724 1139

2.0

Plextol® D498 p(nBA/MMA)

mixed with cadmium yellow
before (a), after 31 days of UV
ageing (b), and 83 days of UV
ageing (c)
1.5

1064
Absorbance Units

1233

985
1.0

1447 841
1385 755
c)

2954
0.5

2874 b)

a)
0.0

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1
UV ageing studies on acrylic binding media
polyethoxylated surfactants after 83 days of UV ageing.
Especially when Primal® AC33 was mixed with cadmium
yellow (Fig. 12), cadmium red (Fig. 8), as well as rutile
(Fig. 9) and anatase (Fig. 13), the absorption of the C–H
stretching band at 2,888 cm−1 decreased while other two
peaks at 2,950 and 2,980 cm−1 corresponding to the C–H
stretching were formed. Additionally, the C–H bending peak
at 1,343 cm−1, the C–C stretching peak at 963 cm−1, and the
C–O peak at 1,109 cm−1 disappeared after 83 days of UV
ageing. Further changes of the absorption spectrum related to
the photooxidative processes are shown by Plextol® D498
mixed with blue ultramarine (Fig. 10): two peaks at 1,144
and 1,111 cm−1 corresponding to the C–O stretching and
another peak at 846 cm−1 related to the C–H rock
progressively decreased. This effect related to the bands at
1,111 and 846 cm−1 can be connected to the loss of ester
group, in agreement with the reduction of C=O absorption
and to the fast oxidative chain scission of the polyethoxy-
lated surfactants when exposed to UV light [22, 35].
In contrast to all other pigments, all principal absorptions
gradually increased in the case of cadmium yellow mixed
with the Plextol® D498 (Fig. 14) and especially in
combination with Primal® AC33 (Fig. 12) corresponding
to increases absorption of the ester side groups.
Conclusions
Before UV exposure, the Py-GC/MS analyses of the
investigated polymers identified two different types of
acrylic emulsions: poly(ethyl acrylate/methyl methacrylate)
copolymer, p(EA/MMA) in Primal® AC33, and poly(n-
butyl acrylate/methyl methacrylate) copolymer, p(nBA/
MMA) in Plextol® D498. The presence of a polyethoxy-
lated surfactant was detected in both acrylic emulsions by
FTIR-ATR and by plotting the single ion chromatogram of
the marker ion fragment of octyl phenol. Additionally, octyl
phenol has been determined in Plextol® D498 by the
double-shot technique in the thermal desorption mode. A
phenolic antioxidant in pure Plextol® D498 matrix could
be detected by the double-shot technique. The identifica-
tion of this additive is significant due to its importance for
the stability of acrylic materials during photooxidative
processes.
After UV exposure, FTIR-ATR recorded newly formed
products including unspecific aldehyde, lactones, and acidic
oxidation products. Unfortunately, these products could not
be identified by Py-GC/MS. A clearly visible difference
after UV exposure is the complete disappearance of the
phenolic antioxidant in Plextol® D498 obtained by double-
shot, thermal desorption mode, which suggests that this
material showed minor UV stability compared with
Primal® AC33. All alteration processes are more pro-
2975
nounced in acrylic binding media mixed with pigments,
which obviously increase the reactivity of the acrylic
binding media. The specific FTIR-ATR results indicate that
each particular pigment induces characteristic reactions
with the binding media under UV exposure.
The present study shows that the double-shot technique
of Py-GC/MS enabled the detection of an additive in
unaged Plextol® D498, otherwise unnoticed by single-shot
technique, but—possibly because of too high thermal
desorption temperature applied—it failed for the identifica-
tion of volatile compounds, which were recorded in aged
samples by FTIR-ATR.
Acknowledgements This work has been funded by Regione
Sardegna (Italy), “Programma Master and Back anno 2009” Alta
Formazione and the Austrian Science Fund, Project no. L699-N17.
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