Studies in Conservation

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The analysis of synthetic paints by pyrolysis–gas

chromatography–mass spectrometry (PyGCMS)

Tom Learner

To cite this article: Tom Learner (2001) The analysis of synthetic paints by pyrolysis–gas
chromatography–mass spectrometry (PyGCMS), Studies in Conservation, 46:4, 225-241, DOI:
10.1179/sic.2001.46.4.225

To link to this article: https://doi.org/10.1179/sic.2001.46.4.225

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 THE ANALYSIS OF SYNTHETIC PAINTS BY PYROLYSIS-GAS
CHROMATOGRAPHY-MASS SPECTROMETRY (PyGCMS)
Tom Learner

Summary- This paper describes the application of pyrolysis-gas chromatography-mass spectrometry

(PyGCMS) to the characterization of an extensive range of synthetic paint types. Household and industrial
paints, both of which have been formulated with polymers such as alkyd, polyvinyl acetate (PVA) and nitro-
cellulose, are included in this study, in addition to the acrylic solution and acrylic emulsion paints that were
made specifically for the artists' market. The pyrograms obtained by PyGCMS were characteristic to each
paint type and their principal diagnostic features are discussed. Apart from using the mass spectra produced
by electron impact (EI) to confirm the identity of every peak, two additional analytical features of the mass
spectrometer were shown to be particularly useful in this study. Chemical ionization (CI) was used to assist
with the identification of unknown peaks through molecular weight determination. Selected ion current (SIC)
monitoring, where the mass spectrometer only scans for specific masses, was successfully used for the detec-
tion of peaks of low intensity or those hidden by a more abundant material with a similar retention time.

Introduction
Despite the frequent incorporation of synthetic
polymers in paint formulations for over 50 years,
only a limited amount of research has been carried
out into appropriate analytical techniques for their
identification on works of art. Many of the tech-
niques used for traditional medium analysis, such
as gas and liquid chromatography, are not suited to
all these materials because of their high molecular
weights (i.e., they are non-volatile and frequently
insoluble in solvents) and because the diagnostic
components may not be extracted from the polymer
matrix. Nevertheless, these polymeric materials can
be broken down into volatile fragments effectively
through pyrolysis (heat in the absence of oxygen),
. and these fragments can consequently be separated
and identified by gas chromatography (GC). This
technique, pyrolysis-gas chromatography (PyGC),
has been used since the ]960s by forensic scientists
for the identification of synthetic binders in house
paints, car paints and various industrial coatings
[1-4]. Despite its occasional use in the art field dur-
ing the next two decades [5, 6] it was not until the
1990s that PyGC was shown to be capable of iden-
tifying most of the synthetic binders used in artists'
painting materials [7-9].
In establishing a facility for the analysis of mod-
ern paints, the Tate Gallery has followed a similar
approach to these studies but with some key modi-
fications. First, the analytical 'capability' has been
broadened to include paints intended for other
more commercial or industrial markets [10]. Many
such paints, in particular those designed for house-
Received March 2000
Received infinal form March 2001
hold decoration (so-called 'house paints'), have
been used by numerous influential artists, for exam-
ple Gillian Ayres, Peter Blake, Patrick Caulfield,
Willem de Kooning, Richard Hamilton, Ben
Nicholson, Sidney Nolan, Francis Picabia, Pablo
Picasso, Jackson Pollock, Bridget Riley, Pierre
Soulages and Frank Stella [11]. Secondly, a PyGC
instrument has been used that incorporates mass
spectrometry (MS) as the detector. This set-up,
pyrolysis-gas chromatography-mass spectrometry
(PyGCMS) is a far more powerful analytical tech-
nique than PyGC for four main reasons. First, the
interpretation of peaks in PyGC relies totally on
comparing retention times to known standards. The
use of MS allows the confirmation of every peak's
identity without any possible confusion between
two (or more) compounds with similar retention
times. Second, if two (or more) peaks overlap in a
pyrogram, the mass spectrum of that area will con-
tain molecular and fragment ions from every com-
ponent. The analyst is therefore usually alerted to
the possibility of more than one compound being
present in that particular peak, and is more likely
to interpret the pyrogram correctly. Third, it facili-
tates the detection of materials at extremely low
concentrations (i.e., when a peak may be confused
with background noise by PyGC). This can often
be encountered when a small amount of one type
of binding medium is added to modify another. It
is also frequently the case when detecting organic
pigments. Although PyGC has been shown to be
effective in detecting azo and phthalocyanine pig-
ments [12], these organic pigments have extremely
high tinting strengths and so are often present in
minute amounts. Fourth, MS often permits the

Studies in Conservation 46 (2001) 225-241 225


identity of unknown peaks to be deduced. This is of
particular importance with modern binders, when
information on formulations and samples of known
composition (i.e., standard materials) may be quite
impossible to obtain from paint manufacturers for
proprietary reasons.
There is insufficient room here to give a detailed
account of all the types of polymer that are used as
modern paint binders and therefore those that need
to be identified through medium analysis. There is a
vast and complex array of such information avail-
able in the paint technology literature [13-17].
However, this has been somewhat simplified by two
surveys within the conservation profession that
have identified four principal classes of binder:
acrylic, polyvinyl acetate (PYA), alkyd and nitro-
cellulose (NC) [18, 19] and the reader is directed to
these for further information on the structure,
chemistry and uses of each polymer type. As an
overall approximation, the main binder used in the
artists' paint market has been acrylic, although
PYA emulsions, vinyl-acrylic emulsions and alkyd
resins have also been used. There are, however, two
quite distinct forms of acrylic paint. These are often
referred to as acrylic solution, where the acrylic
polymer is dissolved in a mineral spirit or turpen-
tine, and acrylic dispersion (or emulsion), where the
acrylic polymer is dispersed in water with the aid of
a surfactant and other additives. The solution form
was developed in the late 1940s, whereas the emul-
sion form only became available in the late 1950s.
The two types have quite distinct mechanical prop-
erties and exhibit very different sensitivities to
organic solvents and water. It is important, there-
fore, to be able to distinguish between them analyti-
cally. In the house paint market, alkyd resins have
been the principal binder in all oil-based products
since the mid to late 1950s in Europe and slightly
earlier in the USA. The house paint market also
developed water-borne polymer emulsions during
the 1950s, in which both PYA and acrylic have
been used. The choice of binder appears to be
dependent on factors such as cost (acrylic is more
expensive), durability (acrylic is considered more
durable and therefore often used for exterior paints)
and surface finish (acrylic has a superior binding
power and is therefore sometimes used for matt
paints where less binder is present) [20]. NC has not
been used in artists' paint, but was used for early
gloss house paints (often termed 'enamels' or 'lac-
quers') before alkyd resins were fully developed.
The occurrence of NC is currently rather limited to
specific products, such as car re-spray paints (the
initial coating is normally a thermosetting acrylic).
Other polymer. classes, for example polyurethane,
epoxy and silicone resins, are certainly used in paint
formulations but normally only for high-cost indus-
226
T. Learner
trial coatings where high durability and weather-
resistance are required. Although these paints are
not so widely used on works of art, the ideal ana-
lytical technique for modern binding media would
also be able to detect their presence.
An additional feature has been to examine every
paint sample non-destructively by Fourier trans-
form infrared spectroscopy (FTIR) in a diamond
cell [21], before the sample is submitted to analysis
by PyGCMS. Although widely used for traditional
medium analysis, FTIR relies on the running of a
large number of reference materials, against which
the spectrum from a paint fragment can be com-
pared. Much work has therefore been required to
obtain a more relevant set of standards for syn-
thetic paint binders, pigments, and extenders; this
will be discussed in a separate publication. This
paper describes the salient features of PyGCMS
analysis on all the principal classes of synthetic
binder. Unless otherwise stated, all the mass spectra
shown were obtained in electron impact (EI) mode.
Acrylic solutions
The use of PyGC on artists' acrylic solution paints,
such as Magna (Bocour), has been successfully
demonstrated [7, 8]. An extremely simple pyrogram
was produced, consisting of a single peak of n-butyl
methacrylate (nBMA) monomer, which indicated
that the acrylic binding medium is a poly n-butyl
methacrylate (pnBMA) homopolymer, and that on
pyrolysis it undergoes complete depolymerization (a
mechanism common to all polymethacrylates [22]),
as shown in Figure 1.
Figure 2a shows a pYrogram of Paraloid F-10
(Rohm and Haas)-the acrylic binder used in
acrylic solution paints-with the mass spectrum of
nBMA. The two most intense ions in the mass spec-
trum were those of m/z = 69 and m/z = 41, pro-
duced by the fragmentation shown in Figure 3.
Strong peaks at m/z = 87 (from the protonation of
methacrylic acid) and m/z = 56 (from butene) were
also seen. The molecular ion of nBMA (m/z = 142)
was not observed.
The single peak of nBMA was a characteristic
feature in the pyrograms obtained from all acrylic
solution paints examined, apart from those colours
Figure 1 Depolymerization mechanism of pnBMA
on pyrolysis.
Studies in Conservation 46 (2001) 225-241
The analysis of synthetic paints by PyGCMS

a Molecule seen
with Py-GC-MS
•• SO,N(C,H,), SO,(N(C,H,),(MW=258)

., 87 CH,O-Q .. CH,O-Q /
N=N OH - - > NH

TOT
•• 113
c.r
XC,H,NO,CI + '
NH, OH

c.r
XC,H,NOP

Figure 4 Production of the molecule seen in

PyGCMS (MW = 258) from the cleavage of the
••0 1800 PR5 molecule around the azo linkage.
&:3& 19:18

b of m/z = 258, corresponding to cleavage at the pig-

122
ment's azo linkage (Figure 4).

72 2SO
Acrylic emulsions

roT The polymers used in acrylic emulsion media are

'••0
13:12
Figure 2 Pyrogram of (a) Paraloid F-10 (pnBMA
acrylic resin) with mass spectrum of nBMA and (b)
Golden MSA naphthol red paint (expanded in y-
axis) with mass spectrum of the most intense pig-
ment (P R5) peak.
that contained one or more organic pigments from
the class known as the azo pigments. For these,
additional peaks could be detected that could be
attributed to the individual pigment (this was also
the case for all other classes of binding medium).
Figure 2b shows a pyrogram of an acrylic solution
paint containing the azo pigment PR5 ('naphthol
red medium' MSA by Golden), expanded in the y-
axis to reveal three minor peaks later in the pyro-
gram. The mass spectrum of the most intense of the
three peaks (at scan 1885) revealed a molecular ion
CH,
-OC,H, d\.=0- ~-c~o
-------? H2C
+
mlz-142 (MW) mlz= 69
Figure 3 Production of fragment ions of m/z
and 41 in the mass spectrum of nBMA.
chemically distinct from those present in acrylic
solution painting materials. Previous PyGC studies
identified two types in a range of artists' acrylic
emulsion paints [7]: poly(ethyl acrylate/methyl
methacrylate) copolymer, p(EAlMMA), and poly(n-
butyl acrylate/methyl methacrylate) copolymer,
p(nBAlMMA). This study would agree with· the
observation that these two copolymers were the
only pure acrylic emulsions to have been identified
in artists' painting materials. However, a number of
modified acrylic copolymers were also detected,
including copolymers with styrene (so-called
'styrene-acrylic' or 'styrenated acrylic' copolymers)
and those copolymerized with vinyl acetate
('acrylic-vinyl' copolymers).
Although both types of pure acrylic emulsion are
utilized in current paint formulations, over the
years there has been a gradual increase in use of
p(nBAlMMA), as the production of many
p(EAlMMA) emulsions has been terminated. This
is because the principal commercial use of these
emulsions, namely exterior house paints, requires a
hydrophobic material and in general the
p(nBAIMMA) copolymers show a superior
hydrophobicity. Out of 10 brands of acrylic emul-
sion paint obtained in 1993, p(nBAIMMA) was
found to be the binder in four of them, and most
new formulations produced since then have been
CH,
based on this emulsion.
HC=.!
1 +
p(EA/MMA) copolymers
mlz=41 Figure 5a shows the overall pyrogram from Plextol
B-500 (Rahm), one of the p(EAlMMA) emulsions
= 69 to have been used in artists' acrylic paint formula-
tions, but similar pyrograms were produced by the

Studies in Conservation 46 (2001) 225-241 227


a
41
.9
59
1200 1BBB
13:12 19:48
b 155 was identified as ethyl methacrylate (EMA).
55
jj
100 ••0 3DO ••0
US£. 2:12 3:18 5:38
Figure 5 Pyrogram of Plextol B-500, a
p(EA/MMA) emulsion. (a) Overall pyrogram with
mass spectrum of MMA. (b) Detail (up to scan
700) with mass spectrum of EA.
emulsions Texicryl 13-002 (Scott Bader) and Primal
AC-234, AC-634, AC-34, AC-33 and AC-22 (all
Rohm and Haas). Also shown in the overall pyro-
gram is the mass spectrum from the most intense
peak, MMA. The mass spectrum of MMA showed
a similar fragmentation pattern to nBMA seen ear-
lier, with prominent ions at mlz = 69 and 41, but
here the molecular ion (m/z = 100) was clearly visi-
ble. Figure 5b shows a detail from the early part of
the pyrogram (up to scan 700) with the mass spec-
trum of the EA monomer. The ability to separate
the EA and MMA monomers, despite their similar
retention times, is clearly seen in this detail. The
molecular ion of EA (also m/z = 100) was, how-
ever, barely visible and its mass spectrum was dom-
inated by a peak of m/z = 55. This corresponds to
the loss of an ethoxy (OC2H5) group to produce a
CH2CHCO+ fragment ion (Figure 6), indicating a
similar fragmentation mechanism to the methacry-
lates. As with the methacrylates, a further cleavage
resulting in the loss of the c=o group presumably
occurred to produce an ion of m/z = 27, but this
mass was under the lower detection limit of the MS
228
T. Learner
m1F 100 (MW) mlF 55
1••
.5 Figure 6 Production of fragment ion of m/z = 55 in
the mass spectrum of EA.
scanning conditions used (m/z = 35) and was there-
300B
fore not seen.
33:00
In addition, the small peak just visible at scan
This monomer was also observed as a minor pyro-
lysis product from pEA homopolymer, so its pres-
ence did not indicate that these emulsions are
terpolymers of p(EA/MMA/EMA).
When the overall pyrogram was considered, the
presence of an acrylate component in the polymer
""if 99
clearly affected the basic depolymerization reaction
that characterized the pyrograms of methacrylate
homopolymers such as pnBMA. It could also be
seen that very little of the overall EA component
(approximately double that of the MMA content)
had been converted to the monomer. Two of the
GOO
6:36 peaks seen later in the pyrogram have been identi-
fied in previous PyGC studies as the EA dimer and
EA trimer (by comparing their retention times with
the pyrogram of pEA homopolymer) [7]. However,
in the same previous study the structures of all
additional peaks (as 'hybrid' dimers and trimers
formed between the two different monomers) could
only be proposed, because the appropriate standard
materials were not available.
The use of PyGCMS, however, enabled struc-
tures to be assigned to all these additional peaks.
Figure 7a shows a detail around the EA trimer
(between scans 1350 and 1700) with two different
mass spectra obtained from this molecule. The mass
spectrum on the left was obtained using the MS in
the usual electron impact (EI) mode. The molecular
ion of the EA trimer (m/z = 300) was not visible.
However, when chemical ionization (CI) was used,
this ion was clearly observed. The spectrum on the
right shows the CI mass spectrum of the EA trimer
using ammonia gas. Under CI with ammonia,
materials were ionized by a chemical reaction with
ammonium ions (NH4 +). CI is a much less energetic
process and therefore produced far less fragmenta-
tion of the molecular ion (it is often termed a
'softer' form of ionization). It is a particularly use-
ful modification for determining the molecular
weight (MW) of unknown peaks, although since the
ammonium ion itself has a MW of 18, the molecu-
lar ion indicated was 18 atomic mass units too
Studies in Conservation 46 (2001) 225-241
The analysis of synthetic paints by PyGCMS

a
U
CH3
208 25S
134 oI 0 0
I
0
301
C,H, CH3

EA sesquimer EA-M1v1A sesquimer

318
"'5
m Figure 8 Proposed sesquimer structures of mole-
134 180200
cules of MW 188.

be isomers of two molecules of EA and one of

MMA.
Figure 7b shows a detail (between scans 500 and
135<3 '.00 1450 1500 iSS. ,,,. 1&50
1400) of the minor peaks observed in the vicinity of
11:51 15:Z4 15:57 1&:38 17:03 17:3& 10:89
the EA dimer (the tallest peak in this group at scan
950). Its MW was confirmed as 200 with PyGCMS
b using CI with ammonia. However, the Cl mass
'89
ItU=208
(£A.B_) spectra of the other three peaks only yielded one
nW:o:IBB
20' with the correct MW for a dimer. This spectrum is
shown on the right of the figure and the peak could
therefore be identified as the EA-MMA hybrid
dimer. The MW of the other two peaks was
tat observed to be 188 (the Cl mass spectrum of the
less intense of the two is shown in the left spec-
trum), so neither of these could be dimeric species.
It was therefore proposed that these two molecules
are the EA and EA/MMA 'sesquimers' (i.e., one
and a half monomers), each consisting of a three-
110O 1000 carbon atom backbone with an acrylate/methacry-
8:48 11:80
late group at either end (Figure 8). The more
Figure 7 Pyrogram of Plextol B-500, a intense of these two sesquimers was also observed
p(EA/MMA) emulsion. (a) Detail (scans in the pyrogram of pure pEA and this was there-
1350-1700) with EI (left) and CI (right) mass spec- fore established as the EA sesquimer. The other
tra of EA trimer. (b) Detail (scans 500-1400) with peak, for which the spectrum is shown, was there-
CI mass spectra of EA-MMA sesquimer (left) and fore the EA-MMA sesquimer.
EA-MMA dimer (right). The reason for the production of dimeric and
trimeric species for acrylate-containing acrylics and
not methacrylate polymers has not been fully
high. The molecular ion seen here was at m/z = addressed. However, it seems likely that it must be
318, confirming the MW of the trimer as 300. A connected to the fact that polyacrylates contain ter-
significant peak at m1z = 301 was also observed, tiary hydrogen atoms along their polymer chains,
corresponding to a simple protonation of the which are known to be more prone to abstraction
trimer. With the MW confirmed by Cl, the initial than other hydrogen atoms. If a polymer chain is
El mass spectrum became easier to interpret. For not in a completely linear arrangement then during
example, the highest mass seen in the El spectrum the depolymerization process tertiary hydrogen
at m/z = 255 was indicative of the loss of an ethoxy atoms further up the chain may be abstracted. The
group from the EA trimer. subsequent production of a free radical not on the
Using this method, all three less intense peaks terminal carbon would initiate the production of
around the EA trimer were also observed to have a the various oligomers. The relatively high yield of
MW of 300, thereby confirming their identity as trimers, in particular the EA trimer, could be
trimeric species between EA and MMA (the MW explained by a six-membered orientation that can
of both EA and MMA is 100). Unfortunately, since be achieved during the appropriate hydrogen
both monomers have the same MW, it was not pos- abstraction, illustrated in Figure 9.
sible from MW determination alone to ascertain The dimers would therefore be formed when the
which combination of monomers was present. tertiary hydrogen atom was extracted from the
However, assuming that the pyrolysis mechanism appropriate position. In fact, trace amounts of an
was similar to that undergone by p(nBA/MMA) EA tetramer and a reasonable quantity of the EA
emulsions (see next section), all three peaks would pentamer-the peak at scan 2400-were also

Studies in Conservation 46 (2001) 225-241 229

 T. Learner
a a

:y( ----"..
Rvz-'O 0 l
o
,H
.
55

o
I
R
0 oI 0 ., 73

R
ror
as ~113
b
.(\ "\

~o I I I I
R R R R

••••
&:36
12DO
13=12
,....
J.9=48
Z400
2&:24 •••••
33:ee

mrL!
~ H,C~

00+ 000000
I I I I
R R R

Figure 9 Proposed mechanism for the production of

R
,J f
,
acrylic trimers: (a) H abstraction at C5, then (b) this 551
resultingfree radical species expels the acrylate trimer, ,~ f
,
thereby propagating a further end chain radical.

observed in the pyrograms of p(EA/MMA) copoly- ·'1 , ~ f

~U
"j

mers (as well as pEA). For these to form, the

hydrogen atom from the seventh or ninth carbon
r
respectively from the free radical end would have to
be abstracted. All the oligomers produced by this
mechanism would contain one double bond in their
,
•••
1:136
zoe
Z:1Z
,

Figure 10 Pyrogram from dark green-brown paint

•••
3:1B
,
- ,
4:Z4
,
5..
5:36
50.
6:3&
,

structures.
p(nBA/MMA) copolymers
The p(nBA/MMA) acrylic copolymers that are also
used in artists' paint formulations gave quite differ-
ent pyrograms to those exhibited by the
p(EA/MMA) emulsions. Figure lOa shows the
pyrogram for a sample of the dark green-brown
background colour used on Patrick Caulfield's
Second Glass of Whisky (Tate Collection T06727),
painted in 1992. Caulfield is known to have used
Lascaux acrylic emulsion paints at that time [11],
but the spectrum is typical of all paints based on
this second type of acrylic emulsion. Similar spectra
were observed for the pure acrylic emulsions,
Primal AC-235 and E-1801 (both Rohm and Haas),
Plextol D-528 (Rahm), and Lascaux 360 (Lascaux).
The mass spectrum for nBA is also shown in
Figure lOa, which has some clear similarities to that
seen for EA, in particular the intense peak at m/z =
55. The additional masses at m/z values of 56 and
73 indicated the production of butene and proto-
nated acrylic acid respectively. Figure lOb illustrates
the use of the single ion current (SIC) facility on
the MS, which scans the mass spectra of every peak
and indicates any occurrence of an ion with a par-
from Patrick Caulfield's 'Second Glass of Whisky'
(1992, Tate Collection 7'06727), a p(nBAIMMA)
emulsion paint. (a) Overall pyrogram with mass
spectrum of nBA (the section to the right of scan
900 is expanded in the y-axis by a factor of 3). (b)
Detail (up to scan 700) with SIC scans for m1z =
55, 69 and 78.
ticularmass. It is an extremely useful way of moni-
toring the presence of a particular kind of material
when a diagnostic mass is known. Here the early
part of the pyrogram (up to scan 700) is shown
with SIC scans for m/z = 55 (to identify the acry-
late) and 69 (for the methacrylate). The small peak
at scan 78 was identified as n-butanol. It is interest-
ing to note that this peak was mistaken for the EA
monomer in a previous PyGC study [8]. This incor-
rect interpretation is totally understandable, as n-
butanol and EA monomer have almost identical
retention times, and this clearly illustrates the limi-
tations of PyGC compared to PyGCMS.
As with the p(EA/MMA) emulsions, several
peaks of significant intensity were observed at later
retention times. However, the CI mass spectra were
far more revealing for the p(nBA/MMA) copoly-
mers as the two monomers have different MW val-

230 Studies in Conservation 46 (2001) 225-241

The analysis of synthetic paints by PyGCMS

a with the C1 mass spectra of the two smaller peaks.

,. These revealed MW values of 216 (scan 1075) and
228 (scan 1106), indicative of the nBA-MMA
'" sesquimer and dimer respectively. The two taller
peaks, labelled in the figure, were identified as the
'14
sesquimer and dimer of pure nBA (MWs of 244
10.
and 256 respectively).

Styrene-acrylic copolymers
Copolymers produced from styrene and acrylic
monomers have also been used in painting materi-
als and PyGCMS was able to identify them. On
1709
18:42
••••
22:00
2109
23:86 pyrolysis, polystyrene itself was observed to follow
a depolymerization mechanism to form principally
b the styrene monomer, although small quantities of
217
,,. a dimer and trimer could also be detected. When
present in a styrene-acrylic copolymer, the styrene
monomer remained the principal peak to be
detected from the styrene component. Thl;: pyro-
lIS

lOr
a

78

"
1000
11:00
,....
17:36
rn,

Figure 11 Pyrogram from dark green-brown paint

from Patrick Caulfield's 'Second Glass of Whisky'
(1992, Tate Collection T06727), a p(nBA/MMA)
emulsion paint. (a) Detail (scans 1700-2200) with
CI mass spectrum of a nBAInBA/MMA trimer iso-
lBOO
1~:48
••••
33:88

mer (left) and EI mass spectra ofnBA trimer

(right). (b) Detail (scans 900~1700) with CI mass b
spectra of nBA-MMA sesquimer (left) and nBA-
MMA dimer (right).

ues (MMA == 100, nBA == 128). Figure 11a shows a f

detail of the pyrogram around the trimer peaks
(between scans 1700 and 2200), with the E1 mass
spectrum of the nBA trimer (right spectrum) and
the Cl mass spectrum of the middle of the other
,
three peaks (left spectrum). As with the
p(EA/MMA) copolymers, the pure acrylate trimer
(scan 1953) was again the most intense of the
trimer group. Its MW of 384, deduced from its C1
mass spectrum, confirmed its identity; the highest
mass observed in its E1 mass spectrum, mlz = 311,
,
209
2:12
,
•••
4.:24
,
500
5:30
,
600
6:36
I I
corresponds to the loss of a butoxy group (with a Figure 12 (a) Overall pyrogram of Maimeri Brera
mass of 73). The MWs of the three other trimer acrylic medium, a p(nBMA/styrene/2-EHA) emul-
peaks were all 356, which indicated that three iso- sion, with mass spectra of styrene (left) and 2-EHA
mers of the nBA-nBA-MMA trimer had been (right). (b) Detail (up to scan 700) of pyrogram
formed. from varnish on David Hockney's 'Mr and Mrs
Figure 11b shows the area around the sesquimer Clark and Percy' (1970/1, Tate Collection T01269)
and dimer region (between scans 900 and 1700), with SIC for m/z = 104 and 55.

Studies in Conservation 46 (2001) 225-241 231

 T. Learner

gram shown in Figure 12a was obtained from Brera

gloss medium (Maimeri); similar pyrograms were
observed for all colours of the Brera acrylic paint
~ II .---1 II 1--> ~
range, apart from those containing azo pigments OCOCH, OCOCH,
H H
where additional peaks were seen. Three major + nCH,COOH
peaks were observed and the (EI) mass spectra of
two are shown here. The first (left spectrum) was Figure 13 First step of the side group elimination
identified as styrene, which displayed an intense mechanism of PVA on pyrolysis, resulting in the
molecular ion at m/z = 104 and little fragmentation elimination of ethanoic acid. The second step involves
(a characteristic of many aromatic compounds), the production of benzene from rearrangement reac-
and the second (right spectrum) was identified as 2- tions along the polyene backbone.
ethylhexyl acrylate (2-EHA) monomer. As with the
other acrylate monomers, the fragment ion of 2- high boiling point hydrocarbons such as those
EHA at m/z = 55 was the most intense peak in the found in waxes). Use of PyGCMS was therefore
spectrum (Figure 6). The most intense peak in the particularly beneficial over PyGC in that the pres-
pyrogram (scan 450) was identified as nBMA and ence of benzene could be confirmed. Figure 14a
the emulsion was therefore characterized as a shows the overall pyrogram from Emultex VV536
p(nBMAIstyrene/2-EHA) terpolymer. (Harco), with the mass spectrum from the intense
A number of the smaller peaks observed in the peak at the start of the pyrogram. This spectrum is
later part of the spectrum were also studied. principally that of ethanoic acid, although the peak
Unfortunately these did not appear in the CI pyro- of m/z = 78 corresponds to the molecular ion of
gram and so many have not been fully identified. benzene. The spectrum of pure ethanoic acid con-
However, various dimeric species between the sists of the three main peaks at m1z = 43, 45 and
monomers were identified from their EI mass spec-
tra, although it is interesting to note that no dimer a
or trimer was seen for either the styrene or 2-EHA
species, despite their formation in significant
amounts on pyrolysis of the respective homopoly-
mers. The following dimers were identified: styrene
dimer (MW 208), styrene-nBMA hybrid (MW 246),
styrene-2EHA hybrid (MW 288) and nBMA-2EHA TOT ?8
so
hybrid (MW 326).
Figure 12b shows a pyrogram of a varnish used
by David Hockney on his painting Mr and Mrs
Clark and Percy from 1970/1 (Tate Collection
TOI269), from which it was possible to detect
another type of styrene-acrylic polymer. Here the
SIC facility was used to scan for m/z = 104 (for
styrene) and m1z = 55 (for acrylates). The two b
•••
6:3&
1200
13:12 .-
19:48

peaks observed in the central part of this pyrogram

were identified as styrene and nBA respectively. The
early peaks were identified as MMA and n-butanol,
and the varnish was therefore characterized as a
p(nBAIMMAIstyrene) terpolymer.
-1, ,~J""""""""""""""" f
Polyvinyl acetate (PV A) emulsions
PVA paints are almost all formulated as water-
borne emulsions (although solution paints can cer-
.l.. .1""""",..1
tainly be produced). Irrespective of this, on
pyrolysis they all produced principally ethanoic
(acetic) acid and benzene, via a side group elimina-
'1."", 50
0:33
L""""""""",
100
1:86
150
1:39
208
2:12
2S8
2:15
,""""
aee
3118
3SO
3:Ejl
f
tion mechanism shown in Figure 13. Figure 14 Pyrogram of Emultex VV536 PVA emul-
Ethanoic acid and benzene had very similar sion. (a) Overall pyrogram with mass spectrum of
retention times when using a non-polar GC column ethanoic acid/benzene peak. (b) Detail (up to scan
(which is used so that it can effectively separate out 400) with SIC for m/z = 45 and 78.

232 Studies in Conservation 46 (2001) 225-241

The analysis of synthetic paints by PyGCMS

60 (in decreasing intensity). The last mass is the a

molecular ion and the two fragments are produced 87 149

on loss of an -OR or -CR3 group respectively. 41

Figure 14b shows the early part of the pyrogram

(up to scan 400) with the SIC facility scanning for
m/z = 45 and 78, revealing the presence of ethanoic
acid and benzene. The ethanoic acid peak was typi- roT 41 164 223 278
cally a strongly fronting peak (a characteristic
observed for all polar organic acids) whereas the
benzene peak was usually reasonably sharp. In
diagnosing the presence of a PVA medium it was
found crucial to be able to confirm the presence of
benzene, as ethanoic acid (without benzene) was ••• 180 • 2400
6:36 19:48 26:24
also produced from the pyrolysis of other polymers,
such as cellulose acetate and the ethylene vinyl b
acetates (EVAs).
It was usually possible to confirm the presence of
an emulsion form of PVA (as opposed to a solution
form) by the detection of a plasticizer, since pure
To,1" .. ~" 1 ,:11'1 •• , I"."""~",,, r
PVA is slightly too hard to form a continuous film
from an emulsion. A number of different plasticiz-
ing methods have been used for this since the intro-
..1,,.~Jld':'''''.,,' ,,,,.. .""""""", f
duction of PVA paints, and PyGCMS was able to
differentiate all the principal types. In early emul- 551" l,""""",,,,,,"",,,.
i''''' r
sion formulations, an 'external' plasticizer, such as
dibutyl phthalate (DBP), was added, often in
appreciable quantities (up to 20% by weight) [23].
The problems caused by these plasticizers migrating
··1 I l
••
~I"

Q:33
"1
~
1:06
f~
'I'

1:39
':,.
~
I

2az
I '"
~I"

2=45
I
~I""

3:tB
~I

3:51
'" I

out of the paint film were overcome during the

1960s by the copolymerization of PYA with softer
monomers, often called 'internal' plasticization.
This has been achieved with a variety of other vinyl
monomers, including some of the softer acrylates,
such as pnBA or p(2-ERA), but it is perhaps most
commonly achieved with 'vinyl versatates' or
'VeoVa' monomers (Shell), which are commercial
mixtures of highly branched C9 and ClO vinyl esters
[24]. The C=C double bond in the structure of
vinyl versatate permits its copolymerization with
vinyl acetate by a simple addition polymerization,
and the resulting copolymer is softer (more plasti-
cized) than PVA homopolymer. These PVAlVeoVa
copolymers are used for many interior household
emulsion paints in the UK (the form in which they
are most frequently encountered on paintings) and
are also used in Flashe paints (Lefranc &
Bourgeois), the only remaining artists' quality PYA
paint product.
On pyrolysis, PVANeoVa copolymer produced
C9 and CIO fatty acids, in addition to ethanoic acid
(and benzene) from the vinyl acetate component,
presumably by a similar side group elimination
mechanism. Figure 15a shows the same pyrogram
as in Figure 14a, but expanded in the y-axis to
show the plasticizer peaks. This PVA emulsion,
Emultex VV536, contains both a vinyl versatate
resin and a phthalate plasticizer (in the majority of
Figure 15 (a) Overall pyrogram of Emultex VV536
PVA emulsion expanded in y-axis with mass spectra
of VeoVa (left) and DBP (right) plasticizers. (b)
Detail (up to scan 400) of pyrogram from red paint
on Andy Warhol's 'Self Portrait' (1967, Tate
Collection T01288) with SIC for m/z = 45, 55 and
69.
PVA emulsions only one kind is used). The mass
spectrum shown on the right is that of DBP, with
an intense fragment ion of m/z = 149. This frag-
ment was found to be the characteristic ion of all
dialkyl phthalates, and its extremely high intensity
suggests a stabilized cyclic structure, such as that
shown in Figure 16.
Also seen in Figure 15a is the band of rather
broad peaks (between scans 830 and 950) produced
by the versatate plasticizer. Although these peaks
were clearly not fully resolved, the overall peak pat-
Figure 16 Fragment ion (m/z = 149) formed from
DBP plasticizer. The ion is characteristic of all
dialkyl phthalate plasticizers.

Studies in Conservation 46 (2001) 225-241 233


HO H,C
~~+
I; I paint used by Andy Warhol in Self Portrait (Tate
o H,C
m/z= 172 m/z= 87
Figure 17 Production of the characteristic fragment
ion (mlz = 87) in Veo Va resins.
tern did confonn to a very distinctive profile. The
mass spectrum from the most intense peak is shown
(left spectrum), but the mass spectra from several
areas in this complicated region all appeared
remarkably similar and were always dominated by
ions of mlz = 87 and 88, suggesting the presence of
several isomers of a particular molecule. The suspi-
cion that many of the peaks in this region were
from very similar chemical compounds was sup-
ported by the CI analysis of the VeoVa component,
which indicated that all of the components had the
same MW of 172. The appreciable fronting that was
observed for each peak indicated the possibility of
fatty acids, and this MW (172) corresponds with CIO
fatty acids. With EI, the mass fragment of mlz = 87
could be produced by the loss of C6H13 as shown in
Figure 17. The other fragment ion of high intensity
(m1z = 88) is harder to explain, but could result
from the production of 2-methyl propanoic acid
(Le., the addition of a hydrogen atom to the charged
carbon in Figure 17) from a rearrangement reaction.
The VeoVa monomer could therefore be under-
stood to consist of several isomers of the appropri-
ate CIO vinyl ester compound. On pyrolysis, this
component would be likely to undergo a side group
elimination reaction, similar to PVA. Since both the
acetate and versatate side groups would be elimi-
nated from the polymer under this mechanism, the
resulting polyene backbone could therefore undergo
the same further rearrangements, which were char-
acteristic of pure PVA polymers, for example the
production of benzene.
Vinyl-acrylic copolymers
A range of copolymers between acrylic and vinyl
acetate monomers can also be produced and many
are used in paint manufacture. One of the earliest
artists' emulsion paints, New Masters (California),
was a vinyl-acrylic product marketed on the fact
that it was formulated at a much thicker consis-
tency than Liquitex, the pure acrylic emulsion then
available. Other vinyl-acrylic emulsion paints have
included Polyflashe colours (Lefranc & Bourgeois)
and Reeves polymer paint. Pyrolysis of these poly-
mers produced the components from both vinyl
acetate (ethanoic acid and benzene) and the rele-
234
T. Learner
vant acrylic components. Figure 15b shows an early
part of the pyrogram (up to scan 400) from a red
Collection T01288) painted in 1967, and is typical
of the pyrogram observed for New Masters paint.
Here the SIC facility has been used to monitor for
ions of mlz = 45 (ethanoic acid), 55 (acrylate) and
69 (methacrylate). Although not shown in the dia-
gram, benzene was detected using SIC for mlz =
78. The monomers used in this paint were therefore
identified as vinyl acetate, EA and MMA.
Alkyds
Alkyd paints are oil-modified polyester paints that
were introduced in the early 1930s, although it is
thought that they did not make a significant impact
on the paint industry, certainly in the UK, until the
late 1950s. Since then, the vast majority of oil-
based household and industrial paints have incor-
porated an alkyd resin as the principal binder.
Perhaps somewhat surprisingly, they have received
only limited use by artists' colourmen, with Griffin
(Winsor and Newton) being the only full range of
artists' colour available.
Alkyds are produced from three main compo-
nents: a poly hydric alcohol, a polybasic carboxylic
acid and a source of monobasic fatty acid (which is
often added in the form of a drying oil). The princi-
pal polybasic acid used in all alkyd paints is
phthalic anhydride, the dehydration product from
1,2-benzenedicarboxylic acid (ortho-phthalic acid).
Although other acids have been used in some
industrial coatings, phthalic anhydride has been
used almost exclusively in the house-paint market.
For all alkyd paints and resins tested, phthalic
anhydride was the principal peak detected on pyro-
lysis and was therefore used as the diagnostic peak
for alkyd paint. Figure 18a shows the pyrogram of
7504\65 alkyd resin (Croda), a typical ortho-
phthalic alkyd resin, with the mass spectrum of the
very dominant phthalic anhydride peak at scan 958.
The molecular ion (mlz = 148) was clearly seen,
with the most intense peak at mlz = 104 produced
by the loss of CO2,
The mechanism of the formation of phthalic
anhydride was thought to be initiated by the cleav-
age of a c-o bond during pyrolysis, which drove
the elimination of the chain from the second ester
linkage, thus forming phthalic anhydride and an
aldehyde end group on the eliminated chain [25].
This mechanism is shown in Figure 19.
A very small-but severely fronting-peak was
also observed in the pyrogram of ortho-phthalic
alkyds at scan 778. A detail of the pyrogram (up to
scan 2000) is shown in Figure 18b, expanded in the
Studies in Conservation 46 (2001) 225-241
The analysis of synthetic paints by PyGCMS
a
7.
104
TO'
•••
6:36
129 •
13:U
1•••
19:48
2460
26:24
b Modified alkyds
105 73
122
41
77
51
Figure 18 Pyrograms of Croda 7504\65 alkyd resin.
(a) Overall pyrogram with mass spectrum of phthalic
anhydride. (b) Detail (up to scan 2000) expanded in
the y-axis with mass spectra of benzoic acid (left)
and palmitic acid (right).
y-axis so the minor peaks are more easily seen. The
mass spectrum of this severely fronting peak
showed a molecular ion at m/z = 122, and corre-
sponded to benzoic acid. The intense peak of m1z =
105 would be formed by the loss of an -OR group.
Also visible in this detail of the pyrogram were the
two saturated fatty acids (palmitic and stearic) from
the drying oil content. The mass spectrum of
palmitic acid is shown, with a molecular ion
observed at m/z = 256 and characteristic peaks at
masses corresponding to fragmentation at different
points along the hydrocarbon chain. For example,
those at m/z = 73 and 129 corresponded to the
+(CR2)2COOH and +(CR2)6COOH ions respec-
tively. The stearic acid is the small peak at scan
1905. The ratios observed between these two fatty
acids (the P:S ratio) in oil-containing paints was not
found to be very reproducible with PyGCMS and
they were therefore not used to determine identity
of the oil in this study.
The use of PyGC to identify the polyhydric alco-
hol component of alkyd resins has been reported
Studies in Conservation 46 (2001) 225-241
o
aGo o
+
o~
Figure 19 Production of phthalic anhydride from an
alkyd resin on pyrolysis.
[26] but this was also not found to be reproducible.
More recently, an alternative method, involving
methylation during pyrolysis, has been reported for
artists' alkyd paint [9] and this is currently being
••••
33:ee examined.
Alkyd paints are often modified further to improve
certain properties, such as decreased drying time,
increased film hardness and increased water resis-
tance. Two of the more common forms of modifica-
tion are the inclusion of phenylethene (styrene)
and/or methylphenylethene (vinyl toluene, VT) into
the pre-polymerization mix (other modifiers include
diisocyanate, acrylic, epoxy or silicone compounds)
[27].
PyGCMS identified many of these modifications.
For example, the pyrogram obtained from styrene-
modified alkyds, although not shown here, essen-
tially consisted of two main peaks from phthalic
anhydride and styrene monomer. In addition,
smaller peaks from the styrene dimer (scan 1400)
and trimer (scan 2025) were also visible. Figure 20a .
shows the pyrogram observed from the red enamel
paint (known to be Humbrol enamel [11]) used on
Peter Blake's The Masked Zebra Kid (Tate
Collection T01877). The mass spectrum shown is
that of VT, with a very strong molecular ion of m/z
= 118, although there was an equally strong mass
at m/z = 117 from the loss of a hydrogen atom. The
presence of phthalic anhydride at scan 900 sug-
gested the paint was a VT modified alkyd. In fact
the VT peak consisted of two peaks, which became
visible when that area of the pyrogram was
expanded. The mass spectra of these two peaks
were almost identical, indicative of two isomers of
VT, probably the 1,2- (ortho-) and 1,4- (para-) iso-
mers. The two peaks seen at the end of the pyro-
gram were characteristic of the organic red pigment
PR3.
A good example of the analytical power of using
SIC is shown in Figure 20b. This shows a detail
between scans 1900 and 2400, the area around the
earlier and more intense peak from PR3. From
PyGCMS studies of pure VT alkyd resins, it was
known that a series of eight VT trimers should also
be seen in this region (if the monomer has two iso-
mers, then the trimers have eight). Each of these
235

a benzoic acid (along with phthalic anhydride),
"8
'1
TOT
•••
£:3(.
128•
13:12
1000.
19:48
2400
26:24 ••••
33:00
b Introduced in the late 1920s, nitro-cellulose (NC)
Figure 20 Pyrograms of red Humbrol enamel paint,
a VT-modified alkyd. (a) Overall pyrogram with
mass spectrum of VT. (b) Detail (between scans
1900 and 2400) with SIC for mlz = 105.
trimer peaks was seen to have a mass spectrum dis-
playing a weak molecular ion at mlz = 354 but
dominated by a very strong fragment ion at mlz =
105. Although a few of these peaks were just visible
in the pyrogram of the Humbrol enamel paint,
many could not be differentiated from background
noise and some were clearly masked by the intense
pigment peak. However, when the SIC facility was
used to scan for this mass (mlz = 105), all eight
peaks became clearly visible.
Many of the other kinds of modification to alkyd
resins were also identified with PyGCMS. Although
their pyrograms are not shown here, these included:
• Modification with polyurethanes was identified
by the presence of the respective diisocyanate
molecule (see polyurethane section).
• Modification with a silicone resin was detected
by the characteristic profile of the dimethyl-
siloxane homologous series (see silicone resin
section).
• Modification with benzoic acid was diagnosed
by the presence of appreciable quantities of
236
T. Learner
significantly more than was detected with most
unmodified ortho-phthalic alkyds.
• Modification with a polyamide resin to pro-
duce a thixotropic alkyd (or 'non-drip' resin)
was often-but not always-identified by the
presence of cyclopentanone, which was also
observed as the major pyrolysis product of the
polyamide Nylon 6,6.
Nitro-cellulose
paints were the first significant class of synthetic
paint to become commercially available. NC paints
are made from a mixture of cellulose nitrate, a sec-
ond resin and appreciable quantities of plasticizer
(apart from the pigments and extenders). The sec-
ond resin is blended with cellulose nitrate to impart
gloss, adhesion and hardness to the film. Alkyd
resins (see above for structure) are now commonly
used for this, although several other resins have
also been used, including ketone resins, dammar
and shellac. The plasticizer is added to the formula-
tion to confer elasticity on the film without destroy-
ing its hardness, but it also has the effect of
increasing the resistance to light, heat, cold, and
sudden temperature changes [28]. Dibutyl phthalate
(DBP) and dioctyl phthalate (DOP) are frequently
used.
Cellulose nitrate itself did not give any character-
istic peaks with PyGCMS. However, the two addi-
tional components (the second resin and a
plasticizer) were usually detected. With PyGCMS
the presence of NC paint could, therefore, only be
inferred by the detection of appreciable levels of
plasticizer with an alkyd resin, as plasticizers are not
required in pure alkyd paints. The pyrogram shown
in Figure 21a is from the orange paint used on
Jackson Pollock's Yellow Islands from 1952 (Tate
Collection T00436). The pyrogram showed a strong
peak from an alkyd resin (phthalic anhydride) and a
weaker but significant peak at scan 1600, whose
mass spectrum is shown. As discussed in the PVA
section, the intense peak at mlz = 149 is indicative
of a phthalate plasticizer, and the retention time
confirmed it to be DBP. The pyrogram therefore
suggested an NC paint, and indeed the presence of
cellulose nitrate was confirmed by FTIR.
Figure 21b shows the pyrogram obtained from
an early 1990s 'cellulose industrial lacquer' made by
Bolloms. Here a group of additional peaks was
observed after the phthalic anhydride peak between
scan numbers 1950 and 2200. This time the SIC
facility was used to scan mlz = 149 for phthalate
Studies in Conservation 46 (2001) 225-241
The analysis of synthetic paints by PyGCMS

a o
14.
~N~O~ ----> ~N=C=O +HO~
1-' "
H

Figure 22 Mechanism for liberation of isocyanate

group on pyrolysis of polyurethanes.
TD'

less weather-resistant, but are much faster curing,

and are therefore used more frequently for interior
applications [30]. Polyurethanes are often added to
alkyd and acrylic formulations to improve their
durability and are widely used as boat paints.
600
(,,:36
120D
13:12 •••••
19:40
2 ••••
26:24.
300D
33~ao The pyrograms produced from all polyurethane-
containing paints tested contained an intense peak
b from the diisocyanate component, which was liber-
ated from the polymer network on pyrolysis by the
reaction shown in Figure 22.

-1 I I ~ I
, , II
..Jll'
I I . , , t
Figure 23a shows the pyrogram obtained from
the yellow paint used on Phillip King's painted
sculpture Dunstable Reel from 1970 (Tate
Collection T01361). The mass spectrum of the most

'l 14.

,
•••
6:36
,,
1200
~:12
I I ,
1000
19:49
l ,
2400
2f,:24
,
••••
33:00
r
intense peak is shown and was identified as TDI.
The spectrum was dominated by a strong molecular
ion (m/z = 174). In fact two peaks were identified
(the second was just visible to the left of the main
peak). The mass spectra of each of these peaks
were very similar and indicated the presence of two
isomers of TDI (a common mix is 80% 2,4-TDI,
Figure 21 (a) Overall pyrogram from orange paint 20% 2,6-TDI [31]).
on Jackson Pollock's 'Yellow Islands' (1952, Tate Although not shown here, the other diisocyantes
Collection T00436), an NC paint, with mass spec- also gave extremely characteristic mass spectra on
trum of DBP. (b) Overall pyrogram of green pyrolysis. For example, the mass spectrum of MDI
Bolloms nitro-cellulose paint with SIC for m/z = 149. (a single peak in the pyrogram at scan number
1775) contained an intense molecular ion at m/z =
250.
plasticizers. The entire group of peaks appeared to
be some form of phthalate and was presumably
Epoxy resins
present as a commercial blend of phthalate isomers.
Again, FTIR confirmed the product as NC. Epoxy resin paints and coatings are mainly 'two-
pack' systems containing an epoxy resin and a
cross-linking agent. Most epoxy resins (approxi-
mately 85% [32]) are condensation products of
Other synthetic polymer paints
bisphenol A (2,2-bis-[4-hydroxyphenyl]propane) and
epichlorohydrin (chloromethyl-oxirane), and can be
Polyurethanes
produced in a range of molecular weights. The cur-
The term 'polyurethane' covers a wide range of ing (or cross-linking) agent is often a polyamine,
products, but all contain a polyisocyanate compo- but in paint formulations isocyanates are also used
nent. For coatings and paint formulations these are [33]. As with the polyurethanes, epoxies are often
typically diisocyanates, such as diisocyanatomethyl- used to modify the properties or durability of
benzene (toluene diisocyanate, TDI), diphenyl- alkyds and acrylic products.
methane diisocyanate (methylenediphenyl The pyrolysis of all such epoxy-containing mate-
diisocyanate, MDI) and 1,6-hexamethylene diiso- rials liberated bisphenol A, whose structure is
cyanate (hexamethylene diisocyanate, HDI); their shown in Figure 24.
chemical structures are given elsewhere [29]. The Figure 23b shows the pyrogram obtained from
aliphatic diisocyanates such as HDI tend to pro- the white enamel paint used by Frank Stella on his
duce extremely durable and weather-resistant coat- painting Salto nel mio Sacca from 1984 (Tate
ings. Aromatic diisocyanates like TDI and MDI are Collection T07152). The major peak in its pyro-

Studies in Conservation 46 (2001) 225-241 237


a general paint application but can be blended with
174
145
tOT
SIlO 2400
fi~36 2£.:24
b PyGCMS was shown to be an extremely effective
Figure 23 (a) Overall pyrogram from yellow paint
on Phillip King's 'Dunstable Reel' (1970, Tate
Collection T01361), a polyurethane paint, with mass
spectrum of TDI. (b) Overall pyrogram from white
paint on Frank Stella's 'Saito nel mio Sacca' (1984,
Tate Collection T07152), an epoxy enamel, with
mass spectrum of bisphenol A.
gram at scan 1855 was identified as bisphenol A
and its mass spectrum is also shown. The spectrum
was characterized by a molecular ion at m/z = 228
and an intense fragment ion at m/z = 213 (due to
loss of one of the methyl groups).
Silicone resins
The silicone resins that are used in paint formula-
tions are normally formed from mixtures of di- and
trifunctional organosilane monomers by controlled
hydrolysis and condensation. The usual chain-form-
ing unit is dimethylsiloxane, -Si(CH3)P- [34]. Pure
silicone resins are too soft and thermoplastic for
H0-o--t-o-0H
Figure 24 Structure of bisphenol A.
238
T. Learner
harder resins such as alkyds, acrylics and epoxies.
Although not shown, the pyrogram of silicone
resins typically contained a dominant peak at scan
165 from hexamethylcyclosiloxane (with a very
strong peak at mass m/z = 207 due to loss of a sin-
gle methyl group). Also observed was a series of
weaker peaks corresponding to a homologous series
of dimethyl siloxanes (whose mass spectra all con-
tain ions of m/z = 73, 147, 221 and 295).
3000
Conclusions
33:00
analytical method for detecting all the principal
classes of synthetic polymers that have been used as
binding media in paint formulations. Each polymer
class yielded a characteristic pyrogram, so that
complicated co- and ter-polymers could be readily
detected. The main limitation of the technique was
the inability to carry out totally quantitative analy-
sis on any of the copolymers or mixtures of media,
due to the occurrence of often quite complex frag-
mentation reactions on pyrolysis. The use of mass
spectrometry as the detector, however, enabled the
detection of weak or masked peaks and the use of
mixed media by artists. Although not discussed
here, the technique was just as suited to characteriz-
ing synthetic grounds and primers, which are for-
mulated with the same types of polymeric binder. It
was also capable of detecting the main classes of
resin used in synthetic varnishes as well as azo
organic pigments.
Appendix: experimental conditions
Each dried paint or polymer sample (usually in the
region of 20llg) was cut into tiny fragments, which
were then fed into a drop of de-ionized water held
on a ferromagnetic wire (composition: 30% iron,
70% nickel). The water was evaporated to leave the
sample fragments attached directly to the wire. The
wire was then fed into a glass liner, which was
flushed with argon for about 10-15 seconds to
remove any air. The liner (and wire and sample)
was placed inside the pyrolysis chamber, which was
then flushed through with helium for another 10-15
seconds. The vent to the pyrolysis chamber was
closed off, the chamber re-pressurized to 1·8 bar
and the helium carrier gas flow directed down
through the liner and onto the GC column.
The pyrolysis unit used for all PyGCMS work
was a FOM-4LX Curie point system. Pyrolysis con-
ditions: 610°C for eight seconds. The pyrolysis
chamber was kept at 200°C to prevent any conden-
Studies in Conservation 46 (2001) 225-241
The analysis of synthetic paints by PyGCMS
sation of the pyrolysates on the glass liner walls,
and the GC injection port was kept at 180°C.
For all electron impact (EI) work the unit was
mounted directly onto the injection port of a
Hewlett Packard 5890 gas chromatograph, and
interfaced to a Finnigan MAT Incos 50 quadrupole
mass spectrometer. For the chemical ionization (CI)
work, the same type of pyrolysis system was used,
but linked to a Fisons 8000 series gas chromato-
graph which was interfaced to a Jeol DX-303 mag-
netic sector mass spectrometer.
In both GC instruments a BPX-5 (SGE) column
was used, which was a non-polar column with a
silphenylene-modified polysiloxane bonded phase.
Both columns were 25 metres long, O·32/!m internal
diameter and O·l/!m film thickness. The temperature
programme adopted was an initial temperature of
40°C, which was held for two minutes and then
ramped at 1O·Cmin-1 to 350·C, where it was held
for a further two minutes.
The Incos 50 mass spectrometer utilized EI ion-
ization at 70eV, and scanned from mass 35 to 500
every second, which eliminated the detection of any
oxygen, nitrogen and water vapour, which may be
present in the sample itself or from small air leaks.
The Jeol DX-303 mass spectrometer used CI with
ammonia gas, and scanned from 60 to 700 atomic
mass units every 0·8 second. The GC-MS interface
of both instruments consisted of a heated transfer
line that was kept at 250·C. Unless CI is indicated,
all pyrograms and mass spectra shown here were
obtained in standard EI mode.
Data from the Incos 50 were collected on a Data
General DG-lO computer, which controlled the
mass spectrometer. After their accumulation, data
files were converted from a time intensity Finnigan
file (*.TI) to a mass intensity file (*.MI) and
transferred via an Ethernet network cable to a PC.
This enabled more detailed interpretation with
Datamaster 11 (Finnigan MAT) software and a
back-up facility. Data from the Jeol DX-303 were
collected using the Jeol MP-7000 data system.
Acknowledgements
This work was made possible by the extraordinary
generosity of the Leverhulme Trust (who provided
funding for four years research) and the FOM
Institute (which loaned the PyGCMS instrument to
the Tate for this period). The author is extremely
grateful to all those involved, but especially
Professor Jaap Boon from the FOM Institute, who
arranged the loan of the instrument and provided
access to a second PyGCMS instrument for the CI
work. Thanks also go to Jos Pureveen and Gert
Eijkel for all their technical assistance with the set-
Studies in Conservation 46 (2001) 225-241
up and maintenance of the instrument. I would also
like to thank all my colleagues at Tate, but in par-
ticular Stephen Hackney and Joyce Townsend, for
their unfaltering support throughout my research.
Materials and suppliers
Bolloms cellulose paints: J.W. Bolloms & Co. Ltd,
PO Box 78, Croydon Road, Beckenham BR3
4BL, UK.
Brera acrylic paints and mediums: Maimeri Artists
Materials Ltd, Hartlebury Trading Estate,
Hartlebury, nr Kidderminster DYlO 4JB, UK.
Croda resins: Croda Resin Ltd, Crabtree
Manorway South, Belvedere DA17 6BA, UK.
Emultex emulsions: Harco, Hoechst House,
Salisbury Road, Hounslow TW4 6JH, UK.
Flashe paints (Lefranc and Bourgeois): Col Art
Fine Art & Graphics Ltd, Whitefriars Avenue,
Harrow HA3 5RH, UK.
Griffin paints (Winsor and Newton): as for Flashe.
Humbrol enamel: Humbrol Ltd, Marfleet, Hull
HU9 5NE, UK.
Lascaux paints and emulsions: Alois K. Diethelm
AG Farbenfabrik, Zurichstrasse 42, 8306
Bruttisellen, Switzerland.
MSA acrylic paints: Golden Artist Colors Inc., Bell
Rd, New Berlin, NY 13411, USA.
Plextol emulsions: Rahm GmbH Chemische Fabrik,
Kirschenallee, 64293 Darmstadt, Germany.
Primal emulsions: Rohm and Haas (UK) Ltd,
Lennig House, 2 Mason's Avenue, Croydon
CR9 3NB, UK.
Texicryl emulsions: Scott Bader Co. Ltd,
Wollaston, Wellingborough NN9 7RL, UK.
VeoVa resins: Shell, Heronbridge House, Chester
Business Park, Wrexham Road, Chester CH4
9QA, UK.
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Author
TOM LEARNERreceived an MA in chemistry from
Oxford University in 1988 and a Diploma in the
conservation of easel paintings from the Courtauld
Institute of Art, University of London in 1991. He
spent a year as a Getty Intern in the painting con-
servation and scientific research departments at the
National Gallery of Art, Washington DC. Since
1992 he has been a conservation scientist at the
Tate, principally researching analytical techniques
for the characterization of twentieth-century paint-
ing materials. He received his PhD in chemistry
(thesis entitled 'The characterisation of acrylic
painting materials and implications for their use,
conservation and stability') from Birkbeck College,
Studies in Conservation 46 (2001) 225-241
The analysis of synthetic paints by PyGCMS

University of London in 1997. Since then he has newly acquired modern paintings. He was a co-
combined his research as a conservation scientist author of The Impact of Modern Paints (2000).
with practical conservation work on the Tate's Address: Tate, Millbank, London SWIP 4RG, UK.

Resume-Cet article deerit ['utilisation de la chromatographie gazeuse Ii pyrolyse couplee avec la spec-
trometrie de masse pour caracteriser un large eventail de peintures synthetiques. Les peintures d'usage domes-
tique ou industriel formulees Ii partir de polymeres tels que les alkydes, acetates de polyvinyle (PVA) et
nitrocellulose, sont incluses dans cette etude, de meme que les peintures en solution ou emulsion acrylique spe-
cialement confUes comme materiel d'artiste. Les pyrogrammes obtenus etaient caracteristiques de chaque type
de peinture et ['on examine ici leurs principales particularites. En plus de ['utilisation de la spectrometrie de
masse Ii impact electronique pour conjirmer ['identification de chaque pic, deux autres modes de fonction-
nement de la spectrometrie de masse se sont revetes particulierement utiles dans cette etude. L'ionisation chi-
mique a ete utilisee pour aider Ii identifier des pies inconnus par Ie biais de la determination des poids
moteculaires. La detection d'ions determines, lorsque Ie spectrometre de masse ne mesure que des masses don-
nees, a perm is de detecter avec succes des pies de faible intensite ou des pies dissimules sous ceux de materi-
aux plus abondants ayant des temps de retention similaires.

Zusammenfassung-In dieser Arbeit wird die Charakterisierung eine groften Anzahl verschiedener syntheti-
scher (Anstrich-) Farben mit Hilfe der Pyrolyse-Gaschromatographie!Massenspektrometrie (PyGC/MS)
beschrieben. Sowohl industrielle Farben als solche, die im Haushalt benutzt werden, werden unter Verwendung
von Alkyd-, Polyvinylacetat (PVA)- und Nitrocellulosepolymeren hergestellt. In der vorliegenden Studie wur-
den sie ebenso untersucht wie Losungen und Emulsionen auf der Basis von Aerylharz wie sie speziell far
Kiinstlerfarben hergestellt werden. Die bei der Methode entstehenden Pyogramme sind charakteristisch far
jeden Bindemitteltyp. Ihrefiir die Identifizierung der Materialien verwendbaren analytischen Merkmale werden
diskutiert. Abgesehen von der Identifizierung jedes Peaks der Gaschromatogramme durch mit
Elektronenstoft-Ionisation (EI) erhaltene Massenspektren, erwiesen sich in der Studie zwei andere
Moglichkeiten des Massenspektrometers als natzlich: Durch chemische Ionisation (CI) konnten unbekannte
Peaks iiber die Molekiilmassen zugeordnet werden. Durch Beobachtung des spezifischen Ionenstroms be-
stimmter Ionen (Selected Ion Current Monitoring) konnten selbst Peaks geringer Intensitiit oder solche, die
unter breiten Peaks iihnlicher Retentionszeit verborgen waren, bestimmt werden.

Resumen-Este articulo describe la aplicacion de cromatografia gaseosa por pirolisis acoplada a espec-
trometria de masas (PyGCMS) para la caracterizacion de un extensa gama de pinturas sinteticas tanto
domesticas como industriales, que han sido formuladas con polimeros de tipo alquidico, acetato de polivinilo
(P VA) y nitocelulosa. Ademas han sido incluidas en este estudio, pinturas acrilicas en solucion y en emulsion,
especificamente creadas para el mercado artisto. Los pirogramas obtenidos por PyGCMS fueron caracteristi-
cos para cada tipo de pintura y sus principales caracteristicas diagnosticos son comentados. Aparte de usar
espectros de masas producidos por impacto de electrones (EI) para conjirmar fa identidad de cada pico, se
demostraron particularmente tililes en este estudio dos caracteristicas analiticas adicionales del espectrometro
de masas. Ionizacion quimica (CI) fue utilizada en la identificacion de los picos desconocidos a traves de la
determinacion del peso molecular. El control por corriente ionica seleccionada (SIC), donde el espectrometro
de masas solamente busca masas especificas, fue utilizado con ex ito para detectar picos de baja intensidad 0
aquellos ocultos por un material mas abundante con un tiempo de retencion similar.

Studies in Conservation 46 (2001) 225-241 241