Microchemical Journal 124 (2016) 949–961

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Microchemical Journal

journal homepage: www.elsevier.com/locate/microc

Accelerated UV ageing studies of acrylic, alkyd, and polyvinyl acetate

paints: Influence of inorganic pigments
Valentina Pintus a,1, Shuya Wei b, Manfred Schreiner a
a
Institute of Science and Technology in Art, Academy of Fine Arts, Schillerplatz 3, A-1010 Vienna, Austria
b
Institute of Historical Metallurgy and Materials, University of Science and Technology Beijing, 30 Xueyuan Road, 100083 Beijing, China

a r t i c l e i n f o a b s t r a c t

Article history: The stability of two types of acrylic binding media, alkyd and polyvinyl acetate (PVAc), four widely used synthetic
Received 26 March 2015 binders in modern and contemporary art, to UV light also including the UV-B range (315–280 nm, middle UV) for
Received in revised form 25 June 2015 simulating sunlight outdoor conditions was studied and compared by double-shot and single-shot Py-GC/MS,
Accepted 9 July 2015
FTIR-ATR, and colour measurements. Thermally assisted hydrolysis and methylation (THM-GC/MS) analyses
Available online 21 July 2015
were used for the alkyd. Additionally, the influence of inorganic pigments on the photo-oxidative stability of
Keywords:
the binding media was also considered. For this purpose, the binders in their pure form as well as mixed with
Py-GC/MS eight different inorganic pigments (titanium white—anatase and rutile, cadmium yellow, cadmium red, hydrated
FTIR-ATR chromium oxide green, ultramarine blue, raw umber Cyprus, and ivory black) were exposed to the accelerating
Colour measurements artificial UV ageing for different periods of time and analysed before and after UV exposure. After UV ageing, the
Acrylic double-shot Py-GC/MS detected the effect of photo-oxidative processes of the binders in a much more detailed
Alkyd way than by the single shot. For instance, photo-oxidation of the acrylics resulted in a production of oligomers
Polyvinyl acetate even during the thermal desorption step of double-shot Py-GC/MS and in a decrease of the EA and nBA main
monomers in the pyrolysis second step. Contrarily, the aged alkyd samples were mostly characterised by a de-
crease of unsaturated fatty acids and especially by the increase of free ortho-phtalic acid detected by double-
shot Py-GC/MS and THM-GC/MS, which is also reflected in the FTIR-ATR results. On the other hand, an increase
of free acetic acid was observed for the aged polyvinyl acetate by double-shot Py-GC/MS. Colour measurements
recorded a greater sensitivity of the alkyd paints, shown by to the bigger shift of L*, a*, and b* coordinates and
change of E* values. Of additional interest was the higher sensitivity to the UV light for synthetic binding
media in combination with pigments.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Currently, the binding media of most paints consist of synthetic ma-
terials such as acrylic, alkyd, and polyvinyl acetates, resulting in a wide
range of different types with properties, and as a consequence, the ma-
jority of modern and contemporary art is composed of synthetic mate-
rials. Therefore, the investigation of the factors influencing their
ageing behaviour is becoming more and more important in heritage
science. The stability of these binders to UV light in outdoor conditions
is particularly important. UV ageing studies of synthetic paint materials
have been carried out in detail in the last 20 years [1–3], mainly consid-
ering indoor conditions that simulate parameters relevant for art ob-
jects housed in museums, such as wavelengths between 400 and
315 nm (UV-A, near UV). Acrylic binders based on an emulsion and
formed by the four basic components, water, monomer, initiator, and
surfactant, are prone to photo-oxidation mostly by chain scission reac-
tions and cross-linking. The chain scissions tended to prevail over the
E-mail address: v.pintus@akbild.ac.at (V. Pintus).
1
Tel.: +43 1 58816 8680; fax: +43 1 58816 8699.
cross-linking reactions when the alkyl side groups are short [4].
On the other hand, the photo-oxidation of alkyds is similar to that
of oil paints because of their similar chemical composition based
on the addition of monobasic fatty acids into the polyester
conformation—formed by a polyhydric alcohol and a polybasic carbox-
ylic acid. Auto-oxidation of the alkyd can continue with excessive de-
gree of cross-linking producing a very stiff and brittle material, chain
scission with prevalent β-scissions, loss of volatile products such as al-
dehydes, alcohols and carboxylic acids and fading (yellowing) [5]. The
fragments formed by the β-scission reactions can be converted into
free, low molecular weight compounds that can stay in the paint film
or can remain in the network, through other cross-links along the chains
or can be lost by evaporation or by solvent treatment [6]. The photo-
oxidative degradation of polyvinyl acetates (PVAc), which are formed
during the polymerisation of vinyl acetate, follows similar mechanism
steps as those of acrylic polymers, which through chain scission and
cross-linking reactions produces a series of reactive intermediates and
radicals [7].
In contrast to studies based on the photo-oxidation of these synthet-
ic materials induced by the UV light in indoor conditions, the influence

http://dx.doi.org/10.1016/j.microc.2015.07.009
0026-265X/© 2015 Elsevier B.V. All rights reserved.
950 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961
of UV-B light (315–280 nm, middle UV) on the stability/degradation of
materials in artworks exposed to outdoor conditions has been inves-
tigated only rarely. UV-B radiation may cause discolouration, cracks,
and other damage to synthetic materials while the UV-A (400–315 nm,
near UV) is usually considered less harmful to polymers. UV-C (280–
100 nm, far UV) which could cause chain scissions and/or cross-
linking of the chemical structure of the polymers is absorbed by the
atmosphere. Furthermore, volatile compounds, which can be formed
during photo-oxidative reactions and/or any changes, are likewise rare-
ly studied by Py-GC/MS, especially in the double-shot mode [8]. This
technique represents a useful and powerful method for the identifica-
tion and characterisation of volatile compounds, polymeric materials,
and additives [8].
Another issue is that the photo-oxidative stability of synthetic
binders can be influenced by the addition of pigments into the system.
They may either have a protective effect by absorbing and/or screening
the UV light or they may be photo-active and therefore catalyse or accel-
erate the photo-degradation of the polymer [9]. The mechanism by
which pigments may act as photo-sensitisers is not well understood,
and detailed data on the influence of inorganic pigments on the stability
of synthetic paint films are still lacking. Additionally, synthetic paints
are characterised by other components that can also contribute signifi-
cantly to their degradation under UV. Thus UV ageing studies of pure
synthetic binding media does not accurately reflect the UV ageing of
synthetic paints and the exact context of the degradation still remains
unclear in many cases. Therefore, more studies concerning the influence
of inorganic pigments on synthetic binding media are desirable.
Partially based on previous studies [10–12], the aim of this work is to
investigate the stability when exposed to UV light including the UV-B
range for simulating sunlight outdoor conditions of four of the most
widely used binding media in modern and contemporary art, two differ-
ent types acrylic, alkyd, and polyvinyl acetate (PVAc), as well as the ef-
fect of different inorganic pigments on their chemical behaviour. For
this purpose, two types of acrylic binding media, alkyd and polyvinyl
acetate (PVAc) both pure and also mixed in the laboratory with eight
different inorganic pigments (titanium white—anatase and rutile,
cadmium yellow, cadmium red, hydrated chromium oxide green, ultra-
marine blue, raw umber Cyprus, and ivory black) were analysed before
and after UV exposure by the double-shot of Py-GC/MS, single-shot of
Py-GC/MS while thermally assisted hydrolysis and methylation (THM-
GC/MS) analyses were used for the alkyd, FTIR-ATR, and colour mea-
surements. A comparison between the double-shot and single-shot
techniques of Py-GC/MS for their application for UV ageing studies of
modern paint materials was also done.
2. Experimental
2.1. Sample preparation
The investigated binders and mock-up samples are listed in Tables 1
and 2, respectively. Approximately 60 mg of two pure acrylic binding
media (Plextol® D498 and Primal® AC33 purchased from Kremer
Pigmente GmbH & Co. KG, Germany) (Table 1) were cast separately
on glass plates, which produced a dried film thickness in a range of
Table 1
List of the binders investigated and their chemical and technical properties.
Binders
Commercial name Company
Plextol® D498 Kremer® Pigmente GmbH & Co. KG, Germany
Primal® AC33 Kremer® Pigmente GmbH & Co. KG, Germany
Medium 4 Lukas®, Dr. Fr. Schoenfeld GmbH & Co., Germany
Mowilith® 50 Kremer® Pigmente GmbH & Co. KG, Germany
10–20 μm. Additionally, different mock-ups of pure Plextol® D498 and
Primal® AC33 mixed with inorganic pigments (Table 2) such as
titanium white (anatase and rutile), cadmium yellow, cadmium red,
hydrated chromium oxide green, ultramarine blue, raw umber Cyprus,
and ivory black were prepared. Each mock-up was made by mixing
with a paint brush the binder and the pigment in a mixing ratio of
about 3:1. Once a proper paste consistency was obtained, the paint
was cast on glass slides. The dried film thickness of these paint samples
was approximately in the range of 30–40 μm. In total, 12 identical spec-
imens for each pure acrylic binding 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 the samples for
24 hours at room temperature, the glass plates were arranged in the
UV chamber, except for unaged reference samples.
The alkyd Medium 4 (Lukas®, Dr. Fr. Schoenfeld GmbH & Co.,
Germany) (Table 1), was cast on three glass plates, producing a dried
film thickness in a range of 10–20 μm. Alike for the acrylics, the alkyd
oil binding medium was mixed with the selected inorganic pigments
and consequently cast onto glass slides (Table 2). In order to obtain
enough samples for the consequent exposure in the UV chamber,
three identical samples for each pigment mixed with the alkyd binding
medium were made. Similar to the acrylic samples, pure alkyd binding
medium and their mixtures with pigments were left dry for 24 hours
at room temperature.
Polyvinyl acetate Mowilith® 50 (Kremer Pigmente GmbH & Co. KG,
Germany) was chosen (Table 1) for making specimens, which was
dissolved in acetone, cast on glass slides and then allowed to dry at
ambient conditions (average thickness of the paint film was about
10–40 μm). The selected inorganic pigments used for the acrylic
mock-ups were mixed with the polyvinyl acetate Mowilith® 50 to pre-
pare mock-up samples on glass slides (Table 2) and left to dry at room
temperature.
The inorganic pigments used for all mock-ups are products of
Kremer except the white pigments, which are part of the material col-
lection of the ISTA (Institute for Science and Technology in Art) at the
Academy of Fine Arts Vienna.
2.2. UV exposure
UV exposure of the samples was carried out in a UVACUBE SOL 2/
400F UV chamber, produced by Dr. Hönle GmbH UV-Technology,
Germany. The UV light radiation source was supplied by a 910 W/m2
Xenon arc solar simulator with an incorporated H2 filter, which pro-
vides radiation with wavelengths between 295 and 3000 nm thus sim-
ulating sunlight outdoor conditions. The chamber temperature was
48.8 °C. No control of the relative humidity (RH) was possible in the
UV exposure chamber used, therefore the RH varied between 30% and
35% depending on the RH of the ambient atmosphere. The accelerated
UV exposure of the acrylic and alkyd samples was carried out for 31
and 83 days, respectively, while the polyvinyl acetates were UV aged
for 60 days. According to the ASTM 2565 – 99 standard [13], the
exposure time of the specimens under UV light was established from a
long-term evaluation and control of the material. This evaluation
was periodically carried out under an optical microscope to observe
Type of binder Composition Product number
Acryl Acqueous dispersion of a thermoplastic acrylic polymer based on: 76000
poly(n-butyl acrylate / methyl methacrylate), p(nBA/MMA)
Acryl Acqueous dispersion of a thermoplastic acrylic polymer based on: 75200
poly(ethyl acrylate / methyl methacrylate), p(EA/MMA)
Alkyd Solution of alkyd resin in mineral spirit 2224
PVAc Polyvinyl acetate in grainy state 67040
 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961 951

Table 2
List of the mock-up samples investigated and their chemical and technical properties.

Mock–up samples

Binder Chemical Constitution

Pigment Color index:
Color composition of number of
classical name generic name
Acryl: Acryl: pigment pigment
Alkyd: PVAc:
Plextol® Primal®
Medium 4 Mowilith®50
D498 AC33

Titanium white
White anatase TiO2 PW 6 69

Titanium white
White rutile TiO2 PW 6 54

Yellow Cadmium yellow CdS PY 37 21120

Red Cadmium red CdS, xCdSe PR 108 21060

Hydrated
Green chromium oxide Cr2O3•H2O PG 18 44250
green

Blue Ultramarine blue Na8Al6Si6O24•Sx PB 29 45010

Raw umber
Brown Cyprus Fe2O3•H2O, MnO2 PBr 8 40610

Black Bone (ivory) black C, Ca3(PO4)2, CaCO3 PBk 9 47150

any change in the morphology of the surface, by Fourier transform at-
tenuated total reflection (FTIR-ATR) analysis (Section 3.3) and colour
measurements (Section 3.4).
By using the Hönle UV-Meter (Dr. Hönle GmbH UV-Technology,
Germany), it was observed that during the UV ageing of the alkyd sam-
ples, the UV radiation intensity of the xenon lamp reached a value of ap-
proximately 177 W/m2, thus exposing the samples to a more gentle
ageing than the acrylic and polyvinyl acetate specimens. Unfortunately,
the extended use of UV lamps results in a gradual decrease of the inten-
sity over time, which has to be taken into account for the UV ageing
studies.
2.3. Pyrolysis gas chromatography mass spectrometry (Py-GC/MS)
For the UV-B ageing studies, all samples were analysed before and
after UV exposure with double-shot and single-shot Py-GC/MS.
Double-shot Py-GC/MS is based on a two-step analysis: 1) Thermal de-
sorption of the samples at lower temperature to detect volatile com-
pounds and 2) pyrolysis of the same sample as second step.
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. Unlike acrylic and the polyvinyl acetate paints, about
100 μg of alkyd samples were treated with 2 μL tetramethylammonium
hydroxide (TMAH) reagent (25 wt% aqueous solution of TMAH, Sigma-
Aldrich, USA) in the sample cups in order to perform thermally assisted
hydrolysis and methylation (THM-GC/MS) analysis. Py-GC/MS and
THM-GC/MS analyses were performed with a PY-2020iD (Frontier Lab,
Japan) pyrolyzer unit combined with a GCMS-QP2010 Plus (Shimadzu,
Japan). For the analyses of the pure acrylic binding media as well
as those mixed with pigments, the GC/MS unit was equipped with a
capillary column SLB-5ms SUPELCO, USA (30 m length × 0.25 mm
internal diameter × 0.25 μm film thickness) using bonded and
highly cross-linked 5% diphenyl / 95% dimethyl siloxane. Due to the
change of the column after the initial measurements, the Ultra Alloy-5
MS (5% diphenyl / 95% dimethyl siloxane) capillary column with a
0.25 mm internal diameter, 0.25 μm film thickness, and 30 m length
(Frontier Laboratories, Japan) was used for the analyses of the alkyds
and polyvinyl acetates afterwards. NIST 05 and NIST 05s Library of
Mass Spectra were used for the identification of the compounds. The
GC column temperature conditions used for the acrylics and polyvinyl
acetates were as follows: initial temperature 40 °C, held for 5 min
followed by a temperature increase of 10 °C/min to 292 °C. For the
alkyds, the oven initial temperature was set at 40 °C for 5 min, and
then followed with a gradient of 6 °C/min up to 280 °C for 10 min.
The helium gas flow was set at 1 mL/min and mass spectra were record-
ed under electron impact ionisation at 70 eV. For the single-shot analy-
ses, the pyrolysis temperature was set at 600 °C and held for 12 s.
The double-shot parameters were as follows: For the thermal de-
sorption of the pure acrylic binding media and their mixtures with pig-
ments, 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 while for the alkyds the
temperature was set at 50 °C and increased by 20 °C/min to 250 °C. Ad-
ditionally, for the polyvinyl acetates, the temperature was set at 100 °C,
held for 2 min and increased by 20 °C/min to 250 °C and held there for
2 min. The second-step pyrolysis was carried out for all samples at
600 °C and held for 12 s.
2.4. 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 sulphate detector (DTGS) and with a diamond crystal. Spectra
were acquired in a 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® of Bruker
Optics, Germany.
952 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961
The infrared absorptions bands obtained for the investigated pig-
ments were identified by comparing the acquired spectrum of the pig-
ment sample with the reference spectrum of the IRUG (Infrared
Raman Users Group) database.
2.5. Colour measurements
A SPM50 (Gretag-Macbeth AG, Switzerland) instrument was used to
obtain spectra in the visible range. Reflectance measurements were car-
ried 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*) are obtained according to the Commission Internationale
de l’Eclairage (CIE) 2000.
3. Results and discussion
The comparison between the results obtained from unaged and aged
samples reveals that the effects of the photo-oxidative reactions were
most determinable after 83 days of UV exposure. Therefore, the compar-
ison between the results acquired was made between the unaged and
83-day aged samples.
3.1. Impact of UV ageing to the paints
The visual appearance of paint colours is a fundamental characteris-
tic for the evaluation of their state of preservation. Any variation of the
material properties to the influence of UV light can correspond to a
change of colour, opacity, and brittleness. Thus, a systematic investiga-
tion of these chemical changes is an important point of study for the
conservation and restoration of paints.
After the ageing periods, some of the samples showed a slight colour
change and different opacity. The colour and opacity of blue mock-ups
were the most affected by UV light. By scraping samples from the
aged films for analysis, it was observed that they had become more frag-
ile and brittle compared to unaged samples. These changes in their mac-
roscopic properties can be considered characteristic for UV ageing and
can be related to their chemical changes described in the next three
Sections 3.2, 3.3, and 3.4.
3.2. Py-GC/MS analysis of unaged and aged samples
In order to investigate the photo-oxidative deterioration of the sam-
ples when exposed to UV light, each of the unaged and aged acrylic and
polyvinyl acetate (PVAc) binder sample types were analysed by either
the single-shot or double-shot mode of the Py-GC/MS while the ther-
mally assisted hydrolysis and methylation (THM-GC/MS) and the
double-shot mode of Py-GC/MS were used for the analysis of the unaged
and aged alkyd samples.
The pyrograms of the binders that had been mixed with pigments
did not display any difference in the Py-GC/MS results in comparison
to the pyrograms obtained for the pure binders. The Py-GC/MS results
obtained from both aged acrylic binding media mixed with pigment,
as well as those of the aged alkyd and PVAc mock-ups in comparison
with the respective aged binders also did not show any change or for-
mation of new peaks, apart a more pronounced alteration of the binders
themselves described in the following section.
The results achieved with the second-step pyrolysis of double-shot
Py-GC/MS and single-shot Py-GC/MS show that the Plextol® D498 is
based on a co-polymer of n-butyl acrylate (nBA) and methyl methacry-
late (MMA) while the Primal® AC33 is characterised by a co-polymer of
ethyl acrylate (EA) and methyl methacrylate (MMA) [10]. In addition to
the peaks of the main monomers, the pyrograms of each acrylic binder
are also characterised by the formation of several and different oligo-
mers (sesquimers, dimers, and trimers) at higher retention time (RT)
[10]. Oligomers are molecules consisting of few monomer units and
generally formed under pyrolysis conditions in a lesser amount. On
the other hand, the pyrolysis products of the polyvinyl acetate recorded
in the single-shot mode of the Py-GC/MS and shown in Fig. 1c are main-
ly based on acetone (m/z = 43, 58), 1-3 cyclopentadiene (m/z = 39, 66),
acetic acid (m/z = 43, 60), benzene (m/z = 52, 78), and toluene (m/z =
65, 91) [12]. The thermal desorption step of the double-shot mode
allowed the detection of the diethyl phthalate (DEP) type of plasticiser
usually used in PVAc (Fig. 2c). The detection of the Di-tert-butyl
dicarbonate (DTBD) type of reagent is probably due to the impurity of
the PVAc product, as it is also the case for octanone (Fig. 2c).
The main components of the alkyd binder—detected by thermally
assisted hydrolysis and methylation (THM-GC/MS) analysis—are
benzoic acid, methyl ester at RT 17.1 min (m/z = 51, 77, 105, 136),
trimethyl ether of pentaerythritol at RT 19.7 min (m/z = 55, 69, 71,
75, 85, 101, 114, 128), phthalic acid, dimethyl ester at RT 26.1 min
(m/z = 77, 92, 133, 163, 194), and the fatty acids from oil such as
methylated fatty acid peaks related to azelaic acid (2C9:0) at RT
27.7 min, palmitic acid (C16:0) at RT 34.6 min, oleic acid (C18:1) at
RT 37.4 min, stearic acid (C18:0) at RT 37.8 min, and linoleic acid
(C18:2) at RT 38 min. Furthermore, the intermediate oxidation products
of 2-octenal, nonanal, 2-decenal, 2,4 decadienal, 2-undecenal and the
dryer compound 2-ethylhexanoic acid were identified in the thermal
desorption step of the double-shot mode of Py-GC/MS (Fig. 2b [11]).
After 83 days of UV ageing, the main evidence of photo-oxidative
processes on both acrylic binders observed in the thermal desorption
pyrogram of the double-shot techniques are the peaks of the
sesquimers, dimers, and trimers, which were not registered in the
unaged material (Fig. 2a). The thermal stability of the samples has evi-
dently been changed by the photo-ageing processes leading to the pro-
duction of oligomers already detectable during thermal desorption.
Additionally, the most intense peak of n-butyl acrylate (BA) of Plextol®
D498 and of ethyl acrylate (EA) of Primal® AC33 in comparison to the
methyl methacrylate (MMA) peak decreased gradually after UV ageing,
whereas the MMA peak became the most intense one (Fig. 1a). This re-
duction in intensity of the EA and BA peaks shows a higher sensitivity to
photo-oxidation reactions of these monomers compared to a monomer
with lower structural units such as MMA. A further indication for a
photo-oxidation process concerns the octyl phenol polyethoxy ethanol
surfactant. No traces of octyl phenol previously detected in the thermal
desorption step in the double-shot mode were found anymore in the
pyrogram of the aged Plextol® D498 and Primal® AC33 by plotting
the corresponding single ion mass profile at m/z = 135 [10].
After 83 days of UV ageing, one of the main signs of photo-oxidative
processes of the alkyd binder is shown by a decrease of unsaturated
fatty acids such as oleic (C18:1) and linoleic acid (C18:2) followed by a
decrease of oxidation products (cis-9-hexadecenal, cis-9-octadecenal,
and octadecanal) from unsaturated fatty acids and increasing of short
chain products (1-octene and hexanal). Additionally, an increase of dicar-
boxylic acid such as azelaic acid (2C9:0) and suberic acid (2C8:0) was also
detected. These results obtained by THM-GC/MS and second-step pyroly-
sis of double-shot of Py-GC/MS (Fig. 1b [11]) suggest oxidation, cross-
linking, and chain scission of unsaturated fatty acids, meanwhile dicar-
boxylic acid are produced [6,14]. Other indications of the photo-
oxidation of the alkyd binder are given by the total decrease of
the group of aldehydes (2-octenal, nonanal, 2-decenal, 2,4-decadienal,
2-undecenal) and the dryer compound (2-ethylhexanoic acid) priory
detected in the unaged binder by the thermal desorption step of the
double-shot of Py-GC/MS (Fig. 2b), probably due to further oxidation
or cross-linking of such products.
After UV ageing, it was possible to observe an increase of the phthalic
anhydride (PhA) peak in the thermal desorption step of the double-shot
of Py-GC/MS (Fig. 2b). By calculating the peak area ratio of the phthalic
anhydride in the thermal desorption step (PhA1) and in the pyrolysis
step (PhA2), it was possible to see an increase of the PhA1/PhA2 in
the aged alkyd, which indicates that more free ortho-phthalic acid was
formed during UV ageing [11]. The main pyrolysis product phthalic
 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961 953

Fig. 1. Pyrograms of unaged and aged acrylic Primal® AC33 mixed with ultramarine blue (PB29) (a), alkyd (b) [11], and polyvinyl acetate (PVAc) mixed cadmium yellow (PY37) (c), ob-
tained with the pyrolysis step of double shot Py-GC/MS. (Peaks: 1) Benzene, 2) 1-Octene, 3) Hexanal, 4) 2-Methyl-1-pentanol, 5) Heptanal, 6) Benzaldehyde, 7) 1-Decene, 8) Octanal,
9) Octanoic acid, 10) Benzoic acid, 11) Phthalic anhydride, 12) 1 (3H)-Isobenzofuranone, 13) Pentadecane, 14) Benzeneacetic acid ethyl ester, 15) trans-9-Octadecenal, 16) Pentadecane,
17) Tetradecanal, 18) n-Hexadecanoic acid, 19) cis-9-Hexadecenal, 20) cis-9-Octadecenal, 21) Octadecanal, 22) 2-oxo-octadecanoic acid methyl ester, 23) 1,3-Benzenediol, monobenzoate,
24) trans-2-Hexenyl benzoate [11]).

anhydride of the alkyd is generally formed by the cleavage of a C\\O
bond during thermal decomposition of the alkyds based on ortho-
phthalic acid and the rise of phthalic anhydride indicates that free
ortho-phthalic acid was formed during UV exposure. Therefore, the in-
crease of PhA1/PhA2 detected by the double-shot Py-GS/MS in the
UV-aged alkyd may suggest that the carbonyl phthalic ester undergoes
photo-oxidation reactions through Norrish type I reaction. It has been
reported that aromatic polyesters are prone to photolysis and photo-
oxidised by Norrish I photo-cleavage as main initiation step of photo-
degradation [15–19]. Scheme 1 shows 2 different possibilities of cleav-
age of the ester group creating 4 different primary radicals. The mecha-
nism of photo-cleavage indicated in path I illustrates the formation of
carboxyl and alkyl radicals (Ia). The next step (Ib) is based on the ab-
straction of a hydrogen atom by the polymer carboxy radical from the
polymer chain to yield a phthalic acid end group, which under the
same mechanism of photolysis and photo-oxidation pathways of Ia)
954 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961

Fig. 2. Pyrograms of unaged and aged acrylic Primal® AC33 mixed with ultramarine blue (PB29) (a), alkyd (b), [11], and polyvinyl acetate (PVAc) mixed with cadmium yellow (PY37) (c),
obtained with the thermal desorption step of double shot Py-GC/MS.

and Ib) may form free ortho-phthalic acid (1c and 1d). Likely the and abstraction of hydrogen (IIb), cleavage (IIc), and again abstraction
mechanisms of photo-cleavage of path I, the path II displays the final of hydrogen (IId).
formation of free ortho-phtahlic acid (IId) through the initial The photo-oxidation process also affected the chemical stability of
production of acyl and alkoxy radicals (IIa) followed by oxidation the polyvinyl acetate (PVAc) binder. The amount of acetic acid—which
 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961 955

was detected in the aged PVAc with both methods of Py-GC/MS—was
higher than in the unaged ones indicating the degradation of the film
by the UV ageing procedure (Figs. 1c and 2c). The increase in intensity
of the peak related to the acetic acid shows a growth of free acetic
acid, which is in agreement with the Norrish type II mechanism based
on the formation of an excited carbonyl group following absorption of
light [20,21]. Furthermore, a decrease of the peak related to the DEP
type of plasticiser in the binder was observed after UV ageing (Fig. 2c),
according to the slow evaporation of such plasticisers, resulting in em-
brittlement and degradation of the paint film [22,23].
3.3. FTIR-ATR analysis of unaged and aged samples
The FTIR-ATR absorption bands of both acrylics—Plextol® D498 and
Primal® AC33—alkyd and polyvinyl acetates binders are summarised in
Table 3. Some of the selected pigments used for preparing the mock-ups
show characteristic IR absorption bands, which in some cases overlap
the absorption bands of the binders. For instance, the C\\O/C\\C skeletal
vibrations of the binders (1,250–900 cm−1) are masked by the ultrama-
rine blue pigment by the overlapping Al, Si\\O4 asymmetric stretching
bands at 1,069, 986 with a weak shoulder at 1,095 cm−1. Similarly to ul-
tramarine blue pigment, bone black pigment (C, Ca3(PO4)2, CaCO3) masks
the C\\O/C\\C infrared region of the binders with a strong peak at
1,020 cm−1 and two less intense peaks at 1,086 and 960 cm−1 of the
phosphate groups (PO3− 4 ). Moreover, the raw umber Cyprus pigment
based on iron oxide Fe2O3 with water manganese oxide MnO2 has a
band around 1,000 cm−1 of the iron oxides. On the other hand, the cad-
mium red and cadmium yellow pigments do not absorb in the considered
mid-infrared region (4000–370 cm−1).
Generally, the most prominent differences in the absorption bands of
the unaged and aged binders were obtained for the acrylic and alkyd,
while the polyvinyl acetate (PVAc) seemed to be the most stable. Normal-
ly, the differences between the unaged and aged samples were more
prominent when the binders were mixed with the pigments. On the
other hand, after 83 days of UV ageing, the acquired infrared spectra of
the unaged and aged pigments did not show any remarkable difference.
The FTIR-ATR results of the unaged and aged samples are summarised
below and arranged according to the corresponding sample types,
i.e. a) binders and b) mock-ups.
3.3.1. Binders
By considering the following infrared regions, it is possible to de-
scribe the UV degradation of all investigated binders:
O\\H stretching (3,650–3,100 cm−1): A gradual broadening in this
infrared region, probably due to the formation of alcohol groups and/
or hydroperoxidic structures [3], was shown by the UV-aged acrylic
Plextol® D498 and Primal® AC33 binders (Fig. 3a). The acrylic samples
showed a continuing increase in absorption as well as a band broaden-
ing of the OH groups with a maximum peak around 3,495 cm−1 as was
likewise observed in the alkyd resin after the UV exposure (Fig. 3c). The
changing of this infrared region is mostly due to the formation of new
alcohol groups along the fatty acid portion through either ß-scissions
or Norrish type I reactions during the photo-oxidation degradation in
a similar way to the natural and photo ageing of the binder simulating
indoor conditions [24–26].
The unaged and UV-aged polyvinyl acetate (PVAc) binder and mock-
ups did not show any type of absorption in the O\\H stretching region
between 3,650 and 3,100 (Fig. 4c).
C\\H stretching (3,100–2,800 cm−1): After 83 days of UV ageing, the
sharp peak at 2,890 cm−1 of polyethoxylated surfactant of both acrylics
was no longer present according to the Py-GC/MS results (Fig. 3a).
During UV exposure, the methylene groups of the alkyd binder were
prone to diminish possibly through Norrish type I and II reactions [27]
or due to the oxidation of double bonds [27,28], which is shown by a
gradual decrease in absorption in the asymmetric and symmetric
(C\\H)CH2 stretching at 2,926 and 2,855 cm−1, respectively (Fig. 3c).
The weak band of the aromatic _C\\H stretching at 3,070 cm−1 detect-
ed in the alkyd binder did not change after 83 days of UV ageing.
By comparing the C\\H stretching region between 2,800 and
3,100 cm− 1 of the IR spectra of the unaged and aged PVAc binding
medium, no significant changes in the weak absorption of the doublet
of the –CH3 and –CH2 asymmetric stretching vibration at 2,973 and
2,926 cm−1 were noticed (Fig. 4c).

Table 3
ATR infrared absorptions of the acrylics Plextol® D498 and Primal® AC33, alkyd Medium 4, and polyvinyl acetate Mowilith® 50 binders investigated.

Bond type Acrylic Plextol® D498 Acrylic Primal® AC33 Alkyd Polyvinyl acetate (PVAc)

p(nBA/MMA) p(EA/MMA) Medium 4 Mowilith® 50

−1 −1 −1
(cm ) (cm ) (cm ) (cm−1)

O\\H stretching – – 3,495 –

C\
\H stretching – – 3,070 –
2,955, 2,931, 2,874 2,949, 2,888, 2,860 2,926–2,855 2,973, 2,926
2,852 shoulder – – –
C_O stretching 1,726 1,723 1,720 1,729
C_C stretching – – 1,600, 1,580, 1,507, 1,489 –
C\
\H bending – 1,513 – –
– 1,466–1,451 1,465–1,451 1,433
1,449, 1,436 shoulder – – 1,449, 1,435
1,386 1,381 1,385 1,370
1,361, 1,343 1,360, 1,343 – –
C\
\O and C\
\C stretching – 1,279 – –
1,236, 1,159, 1,143 1,240, 1,149 1,254 1,225, 1,120
– – 1,174, 1,166 –
1,115 1,109 1,114
1,063 1,061 1,068, 1,040 –
1,022 shoulder 1,021 1,026 1,018
990 – – –
963 964 974 –
944 – – –
C\
\H rock 842 843 – 844
808 – – 795
– – 774 –
754 759 – –
– – 740–709 –
956 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961
Fig. 3. FTIR-ATR spectra of the acrylic Primal® AC33 and alkyd mixed with raw umber
Cyprus (PBr8), (a) and (b) respectively, and of the alkyd binder (c) before (solid line)
and after UV ageing (pointed line).
C_O stretching (1,750–1,700 cm−1): The difference of the carbonyl
stretching absorption and broadening band in all four different UV-
aged binders are very similar.
The IR spectra of the UV-aged acrylic binders in comparison to the IR
spectra of the unaged samples are characterised by a gradual reduction
of the carbonyl group absorption at 1,726 cm−1, which may be related
to the loss of the butyl group of the Plextol® D498 (Fig. 4a) and ethyl
group of the Primal® AC33. Although a loss of an ester group took
place in the alkyd and PVAc binders during UV ageing with a conse-
quent formation of the free ortho-phthalic acid and free acetic acid,
respectively, the absorption of the carbonyl peak at 1,720 cm−1 in the
alkyd binder as well as at 1,729 cm−1 in the PVAc binder remained un-
changed (Figs. 3c and 4c). This is probably due to the compensation of
the loss of the ester groups with some new carboxyl products absorbing
in the same region and formed by reaction of secondary macro radical
with oxygen [4].
The broadening of the carbonyl stretching band of the acrylics and
alkyd shows the formation of newly photo-degraded products such as
Fig. 4. FTIR-ATR spectra of the acrylic Plextol® D498 [10], alkyd, and polyvinyl acetate
(PVAc) mixed with ultramarine blue (PB29), (a) (b) and (c), respectively, before (solid
line) and after UV ageing (pointed line).
carboxyl acids, ketones, and aldehydes [24–27]. Particularly, the pro-
gressive absorption at 1,773 cm−1 in the acrylics and between 1,600
and 1,710 cm− 1 in the acrylics (Figs. 3a and 4a) and alkyd (Figs. 3c
and 4b) indicates respectively the formation of a γ-lactone structure [3,
4,29] or open chain anhydrides [30] and the growing of unsaturated
molecules with a C_C bond due to the polymer chain scissions [3] or
ketones products as a consequence of the reaction of oxygen molecules
with radicals and followed by ß-scission [31]. In case of the PVAc binder,
the weak broadening of the carbonyl peak in the range between 1,700
and 1,600 cm−1 (Fig. 4c) suggests the increase of free acetic acid [32]
after UV ageing according to the Norrish type II mechanism [33],
corresponding with the results obtained by the Py-GC/MS analysis
with the double shot.
C_C of aromatic ring (1,650–1,450 cm−1): The two characteristic
sharp and intense peaks at 1,600 and 1,580 cm−1 followed by two less
intense and weak peaks at 1,507 and 1,489 cm−1 of the aromatic C_C
stretching of the polybasic acid part of the alkyd did not show any signif-
icant change after UV ageing (Fig. 3c).
C\\H bending, C\\O and C\\C stretching, and C\\H rocking (1,450–
700 cm−1): A gradual reduction of the absorption of the typical peaks
of the PEG type surfactant at 1,343, 1,110, and 963 cm − 1 was ob-
served in both acrylic binders after UV exposure, which agrees with
 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961
the Py-GC/MS results in which no detection of any traces of the surfac-
tant found in the aged samples.
Where the doublet of the most intense symmetric CH2 bending
at 1,465 cm− 1 and the less intense asymmetric CH3 bending at
1,451 cm−1 was shown in the IR spectrum of the unaged alkyd binder,
after UV ageing, the asymmetric CH3 bending of the doublet became the
most intense one, complemented by an increase in absorption of the
symmetric CH3 bending at 1,385 cm−1 (Figs. 3b,c and 4b). The absorp-
tion variation of the CH3 to CH2 may be explained by the decrease of the
fatty acid chain length and increase of short chain products in the aged
alkyd binder due to the chain scission degradation of the unsaturated
portion of the fatty acid in the alkyd structure. This result agrees with
the higher amount of short chain products detected in the aged alkyd
samples by the thermal desorption step of double-shot of Py-GC/MS. A
slight decrease of the C\\O stretching phthalic group at 1,254
and 1,114 cm− 1 was observed after UV ageing of the alkyd binder
(Figs. 3b.c and 4b). As it has already been reported in the Py-GC/MS
Section 3.2, the formation of the free ortho-phthalic acids from the car-
bonyl phthalic ester (Schema 1) may explain the gradual reduction in
absorption of the phthalic C\\O stretching band due to the C\\O bond
scission from the alkyd structure. Furthermore, after UV exposure of
the alkyd binder, it was noticed that the peak at 974 cm−1 of the out
of plane _CH bending of trans-structures gradually became a shoulder
(Fig. 3c), mostly due to the oxidation of the double bonds [27,28] or
possibly through Norrish type I and II reactions [27]. No significant
change was noticed for the aromatic C\\H in plane deformation peaks
Schema 1. Suggested Norrish type I photolysis and photo-oxidation pathways of carbonyl phthalic ester of alkyd.
957
at 1,068 and 1,040 cm−1 as well as the aromatic C\\H out of plane bend-
ing at 774, 740, and 709 cm−1 of the alkyd binder after UV exposure.
Similar to the other infrared regions of the PVAc binder/mock-ups,
no noticeable difference could be determined in the wavelength region
between 1,450 and 700 cm−1 by comparing the unaged and UV-aged
specimens.
3.3.2. Mock-ups
All of the differences in the IR spectra recorded between the unaged
and UV-aged binders were more pronounced in the mock-ups, especial-
ly when both acrylic binders were mixed with the ultramarine blue pig-
ment and when the alkyd binder was mixed with the ultramarine blue
and raw umber Cyprus pigments. Particularly, the absorption bands of
the ultramarine blue at 1,095, 1,067, 988, 688, 653, 580, and 441 cm−1
and of the raw umber Cyprus at 3,175, 1,016, and 890 cm−1 became
more evident in comparison to the absorption bands of the binders
(Figs. 3a,b and 4a–c), mostly due to the photo-degradation of the organ-
ic part in the mock-ups. Furthermore, noticeable changes of the absorp-
tion spectrum of Plextol® D498 mixed with ultramarine blue are shown
by the progressively decrease of the C\\O stretching peaks at 1,144 and
1,063 cm−1 and another peak at 846 cm−1 related to the C\\H rocking
as well as the disappearing of the C\\O stretching peaks at 1,159 and
1,114 cm− 1 (Fig. 4a [10]). This effect related to the C\\O stretching
bands and to the C\\H rocking band may suggest the loss of an ester
group in agreement with the reduction of C_O absorption and to the
fast oxidative chain scission of the polyethoxylated surfactants when ex-
posed to UV light [34,35].
958 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961

In contrast to all of the other pigments, most of the principal absorp- bond in the main chain, no variations were detected in the infrared
tions gradually increased when the cadmium red and particularly the spectra of the UV-aged PVAc mock-ups.
cadmium yellow pigment was mixed with both acrylic binders as well
with the alkyd corresponding to an increase of the ester side groups. 3.4. Colour measurements of unaged and aged samples
Similar to the FTIR-ATR results obtained on the aged polyvinyl ace-
tate (PVAc) binder, no obvious differences could be determined by com- The colour measurement results of all investigated unaged and 83-day
paring the spectra of the unaged and UV-aged PVAc mock-ups. Possibly UV-aged acrylics (Plextol® D498 and Primal® AC33), alkyd, and PVAc
due to the low amount of the acetic acid formed during UV ageing mock-ups and pigments are summarised in Table 4, which includes the
through the Norrish type II mechanism (as shown by the results of the shift in the values of the lightness/darkness (L*), redness/greenness (a*),
Py-GC/MS double-shot method) and complemented by the C_C double yellowness/blueness (b*), and total colour (E*). Additionally, the CIELAB
diagrams shown in Figs. 5 and 6 highlight the pattern change of a* and
b* values after UV ageing, indicating colour changes, while in the left
side of the figure it is possible to see the differences in L* values corre-
Table 4 sponding to the brightening and darkening of the paint films.
Shifts in the L*, a*, b*, and E* coordinates of the acrylic Plextol® D498 (a) and Primal® The ΔL*, Δa*, Δb*, and ΔE* values recorded for the investigated pig-
AC33 (b), alkyd (c), and polyvinyl acetates (d) mock-ups as well as of the pigments
ments show a slight difference in the shift of the L*, a*, and b* coordi-
(e) before and after UV ageing.
nates as well change colour (Table 4). The general behaviour of most
a) of the analysed pigments was given by a slight increase in L* values
Acrylic mock-up (Plextol® D498) ΔL* Δa* Δb* ΔE* 2000 corresponding to a brightening of the pigment during the UV exposure.
Titanium white anatase 1.54 0.41 −0.41 1.20
Additionally, the cadmium yellow pigment had the greatest ΔE* value
Titanium white rutile −0.49 0.12 −0.472 0.56 (ΔE* = 5.58) based on the shift of L* of 6.43 and of a* and b* of −6.75
Cadmium yellow −2.37 −3.56 −6.8 2.54 and −1.71, respectively.
Cadmium red 1.83 −0.68 −4.9 2.63 Generally, the differences in the shift of the L*, a*, and b* coordinates
Hydrated chromium oxide green 3.01 6.11 0.55 3.63
between the unaged and UV-aged mock-ups are more prominent in the
Ultramarine blue −5.71 1.76 0.98 4.23
Raw umber Cyprus −0.54 −2.43 −3.87 3.68 case of the pigments mixed with the alkyd binder, which shows this
Bone (ivory) black) −0.76 0.07 0.22 0.58 binder to be least stable when exposed to UV light. In particular, the ul-
tramarine blue mock-up, and to a slightly lesser extent, the raw umber
b) Cyprus mock-up, had the greatest shift of a* (Δa* = − 28.0) and b*
Acrylic mock-up (Primal® AC33) ΔL* Δa* Δb* ΔE* 2000 (Δb* = 37.36) between unaged and aged samples showing a strong re-
Titanium white anatase 2.31 0.44 0.32 1.59 duction in red and blue, respectively. The ultramarine blue alkyd mock-
Titanium white rutile 0.83 0.11 −0.2 0.57 up had the highest shift of L* (ΔL* = 13.12) towards the brightening.
Cadmium yellow −1.28 −1.59 −9.03 2.00 The brightening of the surface could be explained by smoothing of the
Cadmium red 0.64 −1.46 −2.96 1.22
film surface during UV exposure [4].
Hydrated chromium oxide green −6.16 0.00 1.54 4.78
Ultramarine blue 3.07 0.18 −3.09 2.65
The acrylic Plextol® D489 and Primal® AC33 mock-ups showed sim-
Raw umber cyprus 0.8 −1.64 −2.71 2.56 ilar colour change results, where the ultramarine blue, raw umber
Bone (ivory) black) −1.67 0.05 0.34 1.20 Cyprus, and the hydrated chromium oxide green had the greatest shift
in the values of a*, b*, and L*. In contrast, the colour results for the
c)
PVAc mock-ups changed substantially less than for the alkyd and both
Alkyd mock-up ΔL* Δa* Δb* ΔE* 2000 acrylic mock-ups after UV exposure. This latter result agrees with the
Titanium white anatase −4.02 −0.43 −2.53 3.33 FTIR-ATR results.
Titanium white rutile 2.08 0.45 2.26 2.57 Additionally, all four type of binders mixed with the titanium white
Cadmium yellow −0.86 −1.68 2.70 1.44 anatase were shown to be slightly more sensitive to the UV light than
Cadmium red 3.67 −6.81 −7.23 4.50
Hydrated chromium oxide green −4.08 4.37 2.48 4.70
the titanium white rutile according to the more pronounced difference
Ultramarine blue 13.12 −28.00 37.36 16.01 of the a*, b*, and L* values after UV ageing (Table 4), which is completely
Raw umber Cyprus 11.66 −6.74 −10.84 12.68 in accordance to the literature [36].
Bone (ivory) black) 1.25 0.08 −0.20 0.92
4. Conclusions
d)

PVAc mock-up ΔL* Δa* Δb* ΔE* 2000 The UV photo-oxidative stability—including the UV-B range for
Titanium white anatase 1.29 0.12 −3.74 3.41 simulating sunlight outdoor conditions—of four different binding
Titanium white rutile 0.33 0.16 0.64 0.65 media such as acrylics in two different co-polymer forms (Plextol®
Cadmium yellow −1.43 0.43 −0.17 1.08
D498 and Primal® AC33), alkyd, and polyvinyl acetate (PVAc)
Cadmium red −1.01 −0.01 0.77 0.96
Hydrated chromium oxide green 1.78 −2.56 1.34 2.19 when mixed with different types of inorganic pigments, particularly
Ultramarine blue 1.91 −2.94 0.64 1.98 used in modern and contemporary art, was investigated through
Raw umber Cyprus 1.83 −0.44 −0.88 1.59 the single-shot and double-shot Py-GC/MS, FTIR-ATR, and colour
Bone (ivory) black) −1.28 −0.02 0.05 0.90
measurements.
e)
After UV exposure, these techniques recorded different ageing be-
haviours of the acrylics, alkyd, as well as polyvinyl acetate (PVAc). The
Pigments ΔL* Δa* Δb* ΔE* 2000
double-shot technique of Py-GC/MS was especially effective at detect-
Titanium white anatase 3.00 −0.10 −3.30 3.38 ing the effect of the photo-oxidative reactions in a more precise and de-
Titanium white rutile 4.65 0.43 −1.63 3.14
tailed manner relative to the single-shot method. Depending on the
Cadmium yellow 6.43 −6.75 −1.71 5.58
Cadmium red 3.18 0.50 −0.22 2.94 analysed binder, the comparison between the thermal desorption of
Hydrated chromium oxide green 0.86 3.02 −0.65 1.34 the double-shot technique results obtained from the unaged and aged
Ultramarine blue 1.64 −0.24 −0.71 1.44 samples shows main evidence for photo-oxidative deterioration.
Raw umber Cyprus 4.46 −1.82 −1.33 3.98 Concerning both acrylic binding media, the detection of dimers, trimers,
Bone (ivory) black) −1.07 0.39 1.63 1.84
and sesquimers can be detected at a lower temperature than the normal
 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961 959

Fig. 5. CIELAB diagram of the acrylic Plextol® D498 and Primal® AC33, alkyd, and polyvinyl acetate mock-ups investigated before and after UV ageing showing the shifts of their L*, a* and
b* coordinates.

temperature used for the pyrolysis. This can be considered an effect of
the UV light on the investigated materials, showing the impact of UV
on their thermal stability. Additionally, the total decrease of the non-
ionic surfactant after UV exposure, which was possible to detect in the
unaged binders only by plotting its mass profile in the thermal desorp-
tion pyrogram, was sign of the sensitivity of the acrylic binders to the UV
light. The pyrolysis step of the double-shot Py-GC/MS, as well as the
single-shot Py-GC/MS, showed the higher sensitivity of the BA and EA
monomers of the Plextol® D498 and Primal® AC33, respectively, in
comparison to the MMA monomers by the gradual decrease of the BA
and EA peaks in the pyrograms of the aged binders. On the other
hand, newly formed products including unspecific aldehyde, lactones,
and acidic oxidation products were detected by FTIR-ATR analysis
from both acrylic binders.
The results obtained from the thermal desorption of the double-shot
technique of the unaged and aged alkyd binder showed a higher
amount of phthalic anhydride indicating that more free ortho-phthalic
acid was produced during the UV ageing, which is shown by FTIR-ATR
by the gradual reduction in absorption of the phthalic C\\O stretching
band due to the C\\O bond scission from the alkyd structure. This result
is particularly important because it is the first time this phenomenon
has been detected during photo-oxidative studies of alkyd binders
960 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961
Fig. 6. CIELAB diagram of the pigments investigated before and after 83 days of UV ageing showing the shifts of their L*, a*, and b* coordinates.
and especially because the formation of free ortho-phthalic acid was
induced by the effect of UV light including the UV-B range. Furthermore,
the decrease of unsaturated fatty acid and increase of saturated
dicarboxylic acid was detected by THM-GC/MS and the pyrolysis
second step of the double-shot method. In the thermal desorption
step of double-shot Py-GC/MS of the aged polyvinyl acetate (PVAc)
binder, the detectable amount of acetic acid increased, while the
amount of the DEP type of plasticiser highly decreased in the PVAc
aged samples. This latter result was also evinced by FTIR-ATR by the
broadening of the carbonyl peak.
Apart from more accentuated differences already noticed between
the unaged and aged binders, the results obtained with the double-
shot and single-shot Py-GC/MS did not show any difference between
the unaged and aged mock-ups, whereas the FTIR-ATR results demon-
strated that each pigment induces to each binder a different ageing be-
haviour. For instance, the cadmium yellow pigment mixed with both
acrylics and alkyd seems to promote the formation of ester side groups
during UV exposure, which corresponds to an increase of all principal
infrared absorptions in the IR spectra. Additionally, the colour
measurements demonstrated the higher sensitivity to the UV light of
the alkyd in comparison to the acrylics and PVAc mock-ups showed
by the bigger shift of the main coordinates L*, a*, b*, and E* coordinates.
Thus, the UV ageing of different types of binders either alone or when
mixed with different inorganic pigments shows that their different
chemical composition has a first order effect on their resistance to UV-
radiation.
In this work, the Py-GC/MS technique, especially the double-shot
mode, proved to be suitable for the photo-oxidative ageing studies of
acrylics, alkyd, and PVAc binders, whereas the FTIR-ATR method and
colour measurements provided useful information about the influence
of inorganic pigments on the UV stability of the analysed binding media.
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. We thank Anthony J. Baragona (Institute of
 V. Pintus et al. / Microchemical Journal 124 (2016) 949–961
Science and Technology, Department of Conservation Science, University
of Applied Arts, Vienna, Austria) for helping with the English corrections.
References
[1] T. Learner, O. Chiantore, D. Scalarone, Ageing studies on acrylic emulsion paints, Pre-
prints ICOM Committee for Conservation 13th Triennial Meeting, James & James
(Science Publishers), Rio de Janeiro, 2002. 911–919.
[2] P.M. Whitmore, V.G. Colaluca, The natural and accelerated aging of an acrylic artist’s
medium, Stud. Conserv. 40 (1995) 51–64.
[3] M.J. Melo, S. Bracci, M. Camaiti, O. Chiantore, F. Piacenti, Photodegradation of acrylic
resins used in the conservation of stone, Polym. Degrad. Stab. 66 (1999) 23–30.
[4] O. Chiantore, L. Trossarelli, M. Lazzari, Photooxidative degradation of acrylic and
methacrylic polymers, Polymer 41 (2000) 1657–1668.
[5] K.J. Saunders, Organic Polymer Chemistry, Chapman and Hall, London, 1973.
[6] M. Lazzari, O. Chiantore, Drying and oxidative degradation of linseed oil, Polym.
Degrad. Stab. 65 (1999) 303–310.
[7] J. Ferreira, M.J. Melo, A.M. Ramos, M.J. Avila, Eternity is in love with the productions
of time: Joaquim Rodrigo’s classical palette in a vinyl synthetic medium, in: T.
Learner, P. Smithen, J.W. Krueger, M.R. Schilling (Eds.), Modern paints uncovered,
The Getty Conservation Institute, Los Angeles, 2007 (pp.).
[8] M. Herrera, G. Matuschek, A. Kettrup, Fast identification of polymer additives by
pyrolysis-gas chromatography/mass spectrometry, J. Anal. Appl. Pyrolysis 70
(2003) 35–42.
[9] N.S. Allen, Photofading and light stability of dyed and pigmented polymers, Polym.
Degrad. Stab. 44 (1994) 357–374.
[10] V. Pintus, M. Schreiner, Characterization and identification of acrylic binding media:
influence on UV light on the ageing process, Anal. Bioanal. Chem. 399 (2011)
2961–2976.
[11] S. Wei, V. Pintus, M. Schreiner, A comparison study of alkyd resin used in art works
by Py-GC/MS and GC/MS: the influence of ageing, J. Anal. Appl. Pyrolysis 104 (2013)
441–447.
[12] S. Wei, V. Pintus, M. Schreiner, Photochemical degradation study of polyvinyl ace-
tate paints used in artworks by Py-GC/MS, J. Anal. Appl. Pyrolysis 97 (2012)
158–163.
[13] ASTM International D2565–99 (Reapproved 2008) Standard Practice for Xenon-Arc
Exposure of Plastics Intended for Outdoor Applications.
[14] J. Mallegol, J. Gardette, J. Lemaire, Long-term behaviour of oil-based varnishes and
paints. Photo- and thermooxidation of cured linseed oil, J. Am. Oil. Chem. Soc. 77
(2000) 257–273.
[15] M. Day, D.M. Wiles, Photochemical degradation of poly(ethylene terephthalate). I.
Irradiation experiments with the xenon and carbon arc, J. Appl. Polym. Sci. 16
(1972) 175–189.
[16] M. Day, D.M. Wiles, Photochemical degradation of poly(ethylene terephthalate). II.
Effect of wavelength and environment on the decomposition process, J. Appl.
Polym. Scie. 16 (1972) 191–202.
[17] M. Day, D.M. Wiles, Photochemical degradation of poly(ethylene terephthalate). III.
Determination of decomposition products and reaction mechanism, J. Appl. Polym.
Scie. 16 (1972) 203–215.
[18] T. Grossetete, A. Rivaton, J.L. Gardette, C.E. Hoyle, M. Ziemer, D.R. Fagerburg, H.
Clauberg, Photochemical degradation of poly(ethylene terephthalate)-modified co-
polymer, Polymer 41 (2000) 3541–3554.
961
[19] P. Malanowski, S. Huijser, F. Scaltro, R.A.T.M. van Benthem, L.G.J. van der Ven, J.
Laven, G. de With, Molecular mechanism of photolysis and photooxidation of
poly(neopentyl isophthalate), Polymer 50 (2009) 1358–1368.
[20] J. Lemaire, J. Gardette, J. Lacoste, P. Delprat, D. Vaillant, Mechanism of photo-
oxidation of polyolefins: prediction of lifetime in weathering conditions, in: R.L.
Clough, N.V. Billingham, K.T. Gillen (Eds.), Polymer durability: Degradation stabili-
zation and Lifetime predictions, Boston American Chemical Society 1996,
pp. 577–598.
[21] N.J. Turro, Modern Molecular Photochemistry, University Science Books, Mill Valley,
1991.
[22] M.T. Doménech-Carbó, G. Bitossi, L. Osete-Cortina, J. de la Cruz-Ca˜ nizares, D.J. Yusá-
Marco, Characterization of polyvinyl resins used as binding media in paintings by
pyrolysis–silylation–gas chromatography–mass spectrometry, Anal. Bioanal. Chem.
391 (2008) 1371–1379.
[23] M.F. Silva, M.T. Doménech-Carbó, L. Fuster-Lopeˇız, S. Martıˇın-Rey, M.F.
Mecklenburg, Determination of the plasticizer content in poly(vinyl acetate) paint
medium by pyrolysis–silylation–gas chromatography–mass spectrometry, J. Anal.
Appl. Pyrolysis 85 (2009) 487–491.
[24] R. Ploeger, D. Scalarone, O. Chiantore, The characterization of commercial artist’
alkyd paints, J. Cult. Herit. 9 (2008) 412–419.
[25] R. Ploeger, S. Musso, O. Chiantore, Contact angle measurements to determine the
rate of surface oxidation of artists’ alkyd paints during accelerated photo-ageing,
Prog. Org. Coat. 65 (2009) 77–83.
[26] C. Duce, V. Della Porta, M.R. Tine, A. Spepi, L. Ghezzi, M.P. Colombini, E. Bramanti,
FTIR study of ageing of fast drying oil colour (FDOC) alkyd paint replicas,
Spectrochim. Acta A 130 (2014) 214–221.
[27] F.X. Perrin, M. Irigoyen, E. Aragon, J.L. Vernet, Artificial ageing of acrylurethane and
alkyd paints: a micro-ATR spectroscopic study, Polym. Degrad. Stab. 70 (2000)
469–475.
[28] W.J. Muizebelt, J.C. Hubert, R.A.M. Venderbosch, A.J.H. Lansbergen, R.P. Klaasen, K.H.
Zabel, Aluminum compounds ad additional crosslinkers for air-drying high-solids
alkyd paints, J. Coatings Technol. 70 (1998) 53–59.
[29] N.S. Allen, M.J. Parker, C.J. Regan, R.B. McIntyre, W.A.E. Dunk, The durability of
water-borne acrylic coatings, Polym. Degrad. Stab. 47 (1995) 117–127.
[30] L.J. Bellamy, The infrared spectra of complex molecules, Chapman and Hall, London,
1975.
[31] D. Lien-Vien, N.B. Colthup, W.G. Fateley, J.G. Grasselli, The handbook of infrared and
raman characteristic frequencies of organic molecules, Academic, New York, 1991.
[32] M.T. Doménech-Carbó, M.F. Silva, E. Aura-Castro, L. Fuster-López, S. Kröner, M.L.
Martínez-Bazán, X. Más-Barberá, M.F. Mecklenburg, L. Osete-Cortina, A.
Doménech, J.V. Gimeno-Adelantado, D.J. Yusá-Marco, Study of behaviour on simu-
lated daylight ageing of artists’ acrylic and poly(vinyl acetate) paint films, Anal.
Bioanal. Chem. 399 (2011) 3155–3304.
[33] J.L. Ferreira, M.J. Melo, A.M. Ramos, Poly(vinyl acetate) paints in work of art: a pho-
tochemical approach. Part 1, Polym. Degrad. Stab. 95 (2010) 453–461.
[34] D. Scalarone, O. Chiantore, T. Learner, Ageing studies of acrylic emulsion paints. Part
II. Comparing formulation with poly(EA-co-MMA) and poly(nBA-co-MMA) binders,
Preprints ICOM Committee for Conservation 14th Triennal Meeting, James & James/
Earthscan, The Hague, 2005. 350–358.
[35] P. Whitmore, V. Colaluca, E. Farrell, A note on the origin of turbidity in films of an
artists' acrylic paint medium, Stud. Conserv. 41 (1996) 250–255.
[36] M. Schwartz, R. Baumstark, Waterbased acrylates for decorative coatings, Vincent
Verlag, Hannover, 2001.