2013 Annual Report Conference on Electrical Insulation and Dielectric Phenomena
XPS study on direct detection of passivator Irgamet
39™ on copper surfaces aged in insulating mineral oil
M Facciotti*, A F Holt, A P G V Amaro, R C D
Brown, P L Lewin
University of Southampton, Southampton SO17 1BJ, UK
*Corresponding author e-mail: mf1g12@soton.ac.uk
Abstract - Corrosion of copper conductors in mineral oil
insulated power transformers is a well-known problem in
electrical power management and distribution worldwide.
Recently, some corrosive compounds containing sulfur (e.g.
DBDS, dibenzyl disulfide) have been identified to play an
important role in this process. A common strategy to limit
corrosion, either as precaution or remedy, is the addition of a
passivator (Irgamet 39™, I39™) in the oil, with a recommended
concentration of 100 ppm to protect the surface of conductors
from chemical attack from corrosive oil components. In this
study, samples of naturally non-corrosive oil with different
concentrations of I39™ are used to treat copper surfaces that are
aged under inert atmosphere and analyzed with X-ray
Photoelectron (XPS) to assess directly the effective amount of
passivator covering the surface of metal and its dependence on
the original concentration in oil. The main aim is, therefore, to
determine the effect of the concentration of I39™ originally in oil
on the effective surface coverage of copper conductors to observe
its distribution and to verify the recommended passivator
concentration to be used.
Keywords - corrosive sulfur; X-ray photoelectron spectroscopy;
Irgamet 39; transformers; passivation.
I. INTRODUCTION
High voltage engineering was born in order to guarantee high
performances of the electrical distribution network that has
been facing a continuously growing demand in the last
decades. Like any other network, it is based on equilibria and
relies on some undoubtedly strategic pieces of equipment such
as transformers. An electrical power transformer bases its
operations on the voltage ratio and Faraday-Neumann-Lenz
law of magnetic induction between two conductors to define
the relationship between the induced voltage and the flux [1].
Given that, it is necessary to prevent any other phenomenon
that is not strictly inductive and can affect its normal operation,
such as sparking, corona and breakdowns. Technologically this
problem had been overcome by using insulating fluids and
solids interposed between conductors.
Although different possibilities are available the majority of
transformers in use throughout the world are oil filled using
mineral oil, complying with IEC 60296. The oil serves the dual
purpose of providing insulation and as a cooling medium to
conduct away heat produced due to transformer’s losses [1].
978-1-4799-2597-1/13/$31.00 ©2013 IEEE
Sponsored by National Grid (UK).
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G Wilson, P N Jarman
National Grid, National Grid House, Warwick Technology
Park, Gallows Hill, Warwick CV34 6DA, UK
Unfortunately, the use of mineral oils is not free from
difficulties. Studies have shown that this petroleum distillate
may have tendency to attack copper conductors with which it is
in contact causing their corrosion. Corrosion of conductors is a
serious issue both for dielectric and structural integrity of the
transformer and can ultimately lead to catastrophic and
expensive failures. Other studies showed how the presence of a
specific highly corrosive sulfur compound found in certain
mineral insulating oils, DBDS (dibenzyl disulfide), can result
in enhanced copper sulfide formation on the surfaces of copper
conductors under normal operating conditions in transformers
[2]. Copper sulfides, being ionic compounds, disrupt the
insulating performances and contaminate paper insulation and
oil. To suppress this side effect associated with the use of
certain oils, the most commonly adopted prevention and
remedial strategy is the addition of metal passivators [3]. A
passivator reacts with a metal surface (i.e. copper) blocking or
reducing its reactivity towards an aggressive environment.
Benzotriazole and tolyltriazole (BTA, TTA) were and are
commonly used as copper surface passivators in aqueous
systems [4-5] but their application in hydrocarbon system such
as fuel, lubricants [6] and then insulating oils had to wait until
the problem of the poor solubility of BTA in these media was
solved (Fig. 1). Nowadays the most used passivation agent is
Irgamet 39 (provided by BASF).
N N
N N
Me
N N
H Me
N
BTA (TTA) Irgamet 39
Fig. 1. Benzotriazole, tolyltriazole (dashed) and Irgamet 39 structures.
According to the proposed mechanism, originally developed
for aqueous environment involving a retro-Mannich reaction
(Fig. 2), Irgamet 39 should cleave to give the free benzotriazole
derivative to enable it to attack the metal surface [8].
 N
N III. EXPERIMENTAL
CuI/II N
N
Me Metal bulk N
N a. Me
N An example sample of copper that has been used as substrate
for the passivator is shown below (Fig. 3). Copper bars were
Irgamet 39
CuI/II from real conductor coils originally wrapped three times with
H2O/H+
Metal bulk
insulating paper (30x6x3 mm). The copper was washed with
cyclohexane twice before being transferred into vials with oil
b. and Irgamet 39. Wrapped samples were unwrapped just before
the experiment to minimize contamination. The oil used, the
N
same in all experiments, was Nynas Nytro Gemini X, a
N
N
naphthenic non-corrosive (IEC60296) fully inhibited mineral
Me H
oil employed in transformers worldwide. To make the reaction
R' O between the passivator and the metal surface easier, the
HN
impregnation phase was performed in 20 mL clear glass
R'
headspace vials with 15 g of a solution of Irgamet 39 in
mineral oil at 60 °C under N2 atmosphere. The actual
Fig. 2. Binding model (a.) and retro-Mannich mechanism (b.) for procedure was carried out in a vacuum oven (Fistreem
Irgamet 39. International Ltd.) and the atmosphere modification was
achieved after three complete pumping cycles (a vacuum gauge
is fitted showing vacuum pulled in a 0-1000 mbar range) and
I. II. X-RAY PHOTOELECTRON SPECTROSCOPY (XPS) subsequent gas flushing to restore atmospheric pressure. A
slight overpressure of N2 was kept to minimize vapour transfer.
XPS is a surface technique that is able to probe the first ten to Samples produced are detailed in Table 1.
twenty atomic layers. Also known as ESCA (Electron
Spectroscopy for Chemical Analysis) this technique has been
developed during the 1960s thanks to the pioneering work of
Kai Siegbahn et al. (Uppsala, Sweden). XPS is an Ultra-High
Vacuum technique (<10-7 Pa) that investigates the top 1-10 nm
of materials being able to determine its empirical formula and,
under appropriate conditions, even the chemical state of atoms
heavier than lithium. During the experiment a focused mono-
energetic X-ray beam is used to irradiate the surface of the
sample that, as a consequence of the photoelectric effect (A.
Einstein, 1905), emits a certain amount of photoelectrons with
a characteristic energy that are collected to produce a spectrum.
The original binding energy of the electrons is calculated
knowing the kinetic energy of the emitted photoelectrons and
the energy of the X-ray used. Together with photoelectrons we
have Auger electrons that are generated by a slightly different Fig. 3. Example of copper conductors: naked and wrapped in insulating
paper.
mechanism. After the emission of the photoelectron the inner
shell of the atom is left in a metastable condition with a
vacancy (aka hole) that is to be filled by an outer shell electron TABLE 1
that “falls” in the inner shell releasing some energy. Most
Experimental conditions
frequently, this energy is dissipated via radiative pathways. In Sample
the alternative non-radiative pathways the energy is much Exposure Irgamet 39 a.
higher. When the latter happens the energy is transferred to Blank Naked 0
another electron within the same atom that is then ejected with
A Naked 100
a characteristic energy. This electron is named Auger after the
discoverer of this phenomenon (P.V. Auger, 1920s). The B Naked 1000
analysis of the spectrum provides therefore information on the b.
C Wrapped 100
nature of the sample surface. Since XPS is very effective in
detecting heteroatoms the strategy chosen was to use the signal D Wrapped 1000
coming from nitrogen atoms within the molecule, in the C – Paper - 100
benzotriazole moiety, as a marker to detect passivator on the
copper surface. Even though a clean copper surface provides D – Paper - 1000
evidence of carbon and oxygen contamination, as direct effect
of atmosphere exposure, no nitrogen sources should be present. a. [mg/kg].
None the less a background signal was collected and b. One layer of insulating paper.
consequently taken into account (Fig. 4).

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 Fig. 4. XPS spectrum of the Blank sample showing a N 1s background signal at 400.1 eV.

All samples were left into the vacuum oven for 24 hours then A summary of results is shown in Table 2 and summarised
taken out of the oil, rinsed carefully in fresh cyclohexane and below (Fig. 5) where mean values of the readings are reported.
the stored in screw top clear glass vials wrapped in clean Standard deviations of the quantifications of the N 1s peak,
aluminium foil. Spectra were collected using a Kratos AXIS based on the noise levels in the detected signal, were of the
ULTRA XPS with monochromatic Al Kα X-ray source with order of ±0.5 at% therefore values at or below this level are
energy of 1486.6 eV. FAT (Fixed Analyser Transmission) possibly due to the noise itself.*
mode was used with pass energy of 80 eV for wide scans and
20 eV for high resolution scans. The slot aperture for all scan TABLE 2
was set at 300x700 μm while the take off angle for the Atomic composition [%] d.
photoelectron analyser is 90° and “hybrid” lens mode was used Sample
C 1s N 1s O 1s
with an acceptance angle of 9°. The samples appeared to be
slightly gassy, probably due to the intrinsic volatility of Blank A 49.9 1.0 27.6
Irgamet 39 at that pressure and the presence of paper samples A 59.4 5.8 24.0
in the chamber, which were also likely to express some
gassing. The pressure achieved was about 8x10-9 Pa. All B 53.9 7.3 23.2
spectra were charge corrected to the main C 1s peak = 285 eV C 53.8 9.5 19.2
and then quantified to compare the amounts of each element
present in the samples. D 58.0 11.1 17.4

C – Paper 64.8 0.5* 34.0

IV. RESULTS AND DISCUSSION D – Paper 67.1 0.4* 32.2
d. Copper and minor elements contaminants not reported (Cu 2p, Cl 2p, Si 2p, S 2p)
A. Naked copper samples
Naked copper samples show the presence of the passivator as a
N 1s peak at 400.1 eV. The increase in the concentration of
Irgamet 39 in the oil used in the impregnation phase seems to
affect the total instrumental response because higher
concentrations produce higher signals.
B. Wrapped copper samples and paper
Spectra of originally wrapped copper samples show the same
features of the naked samples while the N 1s signal appears to
be stronger, suggesting that the presence of paper allows the
reaction between Irgamet 39 and copper to occur more easily.
On the other hand, it can’t be said from data that the paper
layer acts as a reservoir [8-9] for the passivator since no
evidence was found in the spectra collected. Nevertheless,
absence of the N 1s signal on paper could be due to the weaker
interaction existing between it and the passivator that could be
Fig. 5. Atomic percentage of Nitrogen 1s signal detected across the
more readily desorbed in the extreme vacuum conditions set of samples.
applied.

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The samples showed an excellent nitrogen signal that appears
as a single mono-energetic peak even though a differentiation
between slightly different chemical environments of N atoms
in the molecule was expected.
The detection of Irgamet 39 itself confirms the strong nature of
its chemical interaction with copper given that it is not
desorbed at high vacuum levels. The presence of copper signals
shows its presence close to the surface and therefore suggests a
thin or patchy passive film. Copper tends to change its
oxidation state during time probably because of X-ray
irradiation (Cu 2p changes shape over time). Cu LMM Auger
peak was also collected to clarify the oxidation state of copper
and none of the samples appear to be metallic in the top 20-30
nm. Auger peak for metallic copper should be at 918.65 eV
instead of 915.3 eV, where it was found.
The C:N ratio of the benzotriazole moiety of Irgamet 39 is 2:1
while the measured ratio approaches 10:1, consistently with the
samples exposure to air and subsequent unavoidable C
contamination. In these conditions it was not possible to
observe characteristic features of aromatic compounds such as
shake-ups on the adsorbate. The shake up appears as a
consequence of the interaction between the photoelectron
ejected and the delocalized π orbital within the molecule that
leads to a modification in the photoelectron energy. It should
be detected as a small but broad signal 7-10 eV above in
binding energy from the main peak both for C and N. Given
that, the aromatic structure is not likely to fall apart according
to the mechanism assumed therefore further studies are needed.
V. CONCLUSIONS
It is possible to assess directly the presence of Irgamet 39 on
real copper conductors aged in mineral oil using X-ray
photoelectron spectroscopy. This will be vital when studying
the interactions of passivators with the copper surface and
ultimately making accurate predictions on the most suitable
passivation strategies for in-service transformers.
The same analysis seems not applicable to insulating paper at
the present time. In these preliminary experiments the presence
of paper apparently enhances the reaction between Irgamet 39
and copper while the increase in concentration show a lesser
effect. Irgamet 39 is fairly volatile in UHV conditions and can
be pumped away from both copper and paper surfaces if not
attached (e.g. physisorbed or reacted).
Importantly, the copper peak is too complex and noisy to
determine whether the passivator makes a difference to the
chemical state of the copper atoms at the surface.
At 100 ppm the surface seems not to be completely saturated in
passivator even though it’s proved that this concentration is
effective in preventing corrosion in real applications.
Long analysis times tend to modify copper oxidation state and
in these conditions no obvious aromatic features of the
adsorbate are recognizable.
ACKNOWLEDGMENTS
The authors would like to thank National Grid for the financial
support to the project, Emily Smith (University of
Nottingham) who performed XPS analyses (EPSRC Grant
EP/F019750/1 - "A Coordinated Open-Access Centre for
Comprehensive Materials Analysis") and BASF for providing
Irgamet 39 used in the experiments.
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