Conservation issues of modern oil paintings: a

molecular model on paint curing

Ilaria Bonaduce*§, Celia Duce§, Anna Lluveras-Tenorio§, Judith Lee, Bronwyn Ormsby, Aviva

Burnstock† and Klaas Jan van den Berg‡.

§ Department of Chemistry and Industrial Chemistry, University of Pisa, via Moruzzi 13-56124, Pisa,

Italy


Conservation Department, Tate, Millbank, London SW1P 4RG, United Kingdom

† Courtauld Institute of Art, Somerset House, Strand, London, WC2R 0RN, United Kingdom

‡ Cultural Heritage Agency of the Netherlands (RCE), Hobbemastraat 22, 1071, ZC, Amsterdam
CONSPECTUS GRAPHIC
CONSPECTUS

20th- and 21st-century oil paintings are presenting a range of challenging conservation problems

that can be distinctly different from those noted in paintings from previous centuries. These include

the formation of vulnerable surface ‘skins’ of medium and exudates on paint surfaces,

efflorescence, unpredictable water and solvent sensitivity and incidence of paint dripping which can

occur within a few years after the paintings were completed.

Physicochemical studies of modern oil paints and paintings in recent years have identified a range

of possible causal factors for the noted sensitivity of painting surfaces to water and protic solvents,

including the formation of water-soluble inorganic salts and/or the accumulation of diacids at the

paint surface, which are oxidation products of the oil binder. Other studies have investigated the

relationship between water sensitivity and the degree of hydrolysis of the binder, the proportions

of free fatty and dicarboxylic acids formed, as well as the relative content of free metal soaps. Thus

far, data indicate that the qualitative and quantitative composition of the non-polymerised fractions

of the oil binder cannot be solely or directly related to the solvent sensitivity of the paint film.

Conclusions therefore indicate that the polymeric network, formed upon the curing of the oil plays

a fundamental role; suggesting that water sensitivity – at least in some cases - may be related to

the poor development, and/or polar nature of the formed polymeric network rather than the

composition of the non-polymerised fractions.

Poorly developed polymeric networks, in combination with the migration of polar fractions i.e.

dicarboxylic and hydroxylated fatty acids towards the paint surface, can be related to other

degradation phenomena, including the separation and migration of the paint binder which can lead

to the presence of observable skins of medium, as well as the more alarming phenomenon of

liquefying or dripping oil paints. It is thus crucial to understand the molecular composition of these
paints and their physicochemical behaviour to aid the further development of appropriate

conservation and preservation strategies, as the risks currently associated with surface cleaning

treatments and other conservation procedures can be unacceptably high.

This account reviews the relationships between the degradation phenomena associated with

modern oil paintings and the chemical composition of the oil binder; and proposes a molecular

model for the development of water sensitivity and other noted degradation phenomena. It is

suggested that water sensitivity (and possibly other degradation phenomena) are consequences of

processes that take place upon curing, and in particular to the rate of formation and decomposition

of alkoxyl and peroxyl radicals. These reactions are strongly dependent on the type of oil present,

ambient environmental conditions, and the chemical and physical nature of the pigments and

additives present in the paint formulation. When the curing environment is oxidising, the chemistry

of peroxyl radicals dominates the reaction pathways, and oxidative decomposition of the paint film

overwhelms cross-linking reactions.

INTRODUCTION

Cultural Heritage is a non-renewable resource whose preservation, restoration and enhancement

are key to continuous cultural development. Modern painted art chronicles rapid changes within

societies, reflecting technical, political and social developments in recent and current history.

Access to modern and contemporary art for present and future generations is key to identity and a

powerful driver for innovation; however collections are at risk due to unprecedented, and often

unpredictable conservation challenges which largely reflect changes in materials and artistic

practice. In the 18th and 19th centuries, industrialisation led to significant developments in the range
of materials available for use by artists and transferred much of the materials-based knowledge

away from artists to manufacturing. This is most commonly symbolised by the 1841 invention of

the collapsible paint tube, which facilitated painting outside of the studio for the first time,

contributing to the birth of Impressionism. During the 19th C, paint manufacturers developed new

larger-scale technologies for making paint and both manufacturers’ and artists experimented with

paint formulations to achieve a range of visual effects. With homogeneity in rheology and drying

time as key goals, artists’ oil paint manufacturers included a range of materials, including dispersion

agents, plasticizers, fillers, driers and surfactants to paint formulations to create stable paints,

increase shelf life and transportability etc. Across the 20th and 21st centuries, toxic inorganic

pigments have been substituted with benign - and often cheaper - organic colorants to address

health and safety issues, to control cost and to comply with environmental legislation.

Amongst cultural heritage professionals there is a growing awareness of complex conservation

issues affecting painted art produced from the 19th century till now, which are often significantly

different from those presented by oil paintings from earlier centuries.

Degradation issues of modern oil paintings

The pioneering work of J.J. Boon and his co-workers described how, in the course of curing and

maturation of an oil paint film, polymerisation of polyunsaturated glycerides coexist with hydrolysis

of ester bonds, formation of new oxygen-containing functional groups, oxidative cleavage of the

fatty acid hydrocarbon chains, and metal ion co-ordination of the fatty acid group of the cross-

linked material and non-cross-linked fractions1,2. All these reactions were shown to lead to the

formation of paint film containing both mobile and stationary phases1, which have been proven by

numerous authors in the following years to be linked to the appearance and condition of a painting.
 Phenomena regularly observed in modern oil paintings include the formation of vulnerable

‘medium skins’ on paint surfaces (Figure 1), fatty acid and metal soap efflorescence, water- and

solvent-sensitivity, the formation of oil exudates on paint surfaces, delamination of paint layers,

softened paints, and occasionally alarming incidences of dripping paints which have been known to

occur within ten years after painting3.

a) b)

Figure 1 Willem de Kooning (1904-1997), Rosy-Fingered Dawn at Louse Point, oil on canvas, 1963.

Stedelijk Museum, Amsterdam. The surface of this painting is extremely sensitive to solvents and

interaction of the solvent removes the degraded skin of medium, causing loss of surface gloss; a)

Secondary electron image of a sample from the untreated white paint surface, showing medium-

rich organic skin at surface coating the pigment particles beneath; b) Secondary electron image

from a sample taken from the white paint surface after treatment with 0.5% ammonium citrate,

pH6.5: the medium-rich organic skin has been removed, exposing the pigment particles that scatter

light, creating a matt surface on visual inspection (Reproduced with permission from Tempest,

unpublished dissertation Courtauld Institute of Art 2010).

Among the issues encountered, water sensitivity is proving particularly challenging, as the removal
of accumulated, deposited soiling, often known as surface cleaning, traditionally relies upon water
as the key component. In these cases, water may not be safely applied without causing undesirable
surface disruption and pigment pick-up3-7.

Water sensitivity has now been identified in model oil paint samples prepared from raw
materials4,8,9, in samples taken from batches of manufactured paint10, and in several paintings 9-13.
Sensitivity may be limited to certain colours, may affect the whole surface of a painting, may be
specific to some paint brands or lines, and may affect specific pigments across several brands 8,10,13.

Recent research has identified some of the causes and/or contributing factors relating to the

changes observed in modern oils (i.e. water sensitivity and poor drying behaviour) including: the

conversion of magnesium carbonate filler material used in some artists’ paints to water-soluble

magnesium sulphate heptahydrate salts at paint surfaces4 (Figure 2), the migration of polar diacids

to oil paint surfaces6, and in some cases, the use of semi- or non-drying oils such as safflower 14,15

or palm oil16 as the binder or proportion of the binder.

 a)

atmospheric SO2

MgSO4•7H2O
b) crystals

Pigment
MgCO3

Figure 2. a) Secondary electron microscope image of water sensitive cobalt violet oil paint from

Jasper Johns Untitled 1964-’65; Stedelijk Museum, Amsterdam: epsomite crystals are visible

protruding through the surface. b) Schematic representation of influence of atmospheric SO2 (levels

peaked between 1950 - 1970) on paints containing MgCO3, a common additive in modern paints

(used as filler to reduce the amount of pigment, lowering costs). Adapted with permission from

Silvester et all4 Copyright (2014) Taylor and Francis.

Research carried out as part of the JPI Cultural Heritage funded Cleaning Modern Oil Paintings

(CMOP) project17 focussed on characterising water sensitive and non-water sensitive modern oil

paint samples taken from over 50 paintings from the 20th century, and over 70 paint outs among

paint swatches made by paint manufacturers as drying time tests, and model samples prepared

using paints from several artists’ paint manufacturers. One of the research questions within CMOP

was formed from the observation that - especially when water sensitivity cannot be attributed to
the presence of epsomite crystals – aqueous and ethanol extracts of sensitive paints are

characterised by relatively high amounts of dicarboxylic acids10, which are possible peroxide

decomposition products formed upon the curing of a drying oil18. Moreover, it was shown that non-

water sensitive paints (within the limitations of the paints studied) commonly presented a relatively

low degree of oxidation as indicated by the total azelaic acid content, while water-sensitive paints

presented varying degrees of oxidation10,19.

As the group of diacids are inherently more water-soluble than monocarboxylic fatty acids (e.g.

aqueous solubility at 20°C of azelaic acid: 0.01272 mols/L; palmitic acid 0.00003 mols/L), an

hypothesis that water solubility may be related to increased diacid content resulting from a higher

degree of oxidation and hydrolysis of the binding medium, was originally proposed at the beginning

of the CMOP project. Similarly, when metal soaps are formed between the cations of certain

pigments and driers (such as Zn, Pb, Cu), and acidic moieties present in the paint film (produced as

a consequence of oxidation of unsaturated fatty acids, and/or hydrolysis of glycerides), a paint is

less likely to be water sensitive. Fatty acid soaps of alkaline earth or heavy metals are highly

insoluble,20 and are believed therefore to contribute to the stability of the paint film by forming an

ionomer-like network21,22.

Model oil paint samples made with the same type of pigment and oil, the same pigment:medium

ratio and aged under the same conditions, but containing different additives, were observed to

develop varying degrees of water-sensitivity23. Interestingly, for this group of samples, the degree

of water sensitivity did not appear to relate to the total content of dicarboxylic acids (i.e. free

dicarboxylic acids, and those covalently bound to glycerides and metal coordinated to the ionomer

like network, nor the free dicarboxylic acid content, nor the metal soap content of free (non-
crosslinked) fatty and dicarboxylic acids, and to the overall degree of hydrolysis of ester bonds

within the oil medium24.

In a further study of two Winsor & Newton (W&N) artists’ oil paint swatches where the paints

contained the same pigment (phthalocyanine green, PG7), the same blends of oil (linseed and

safflower) and had a closely similar inorganic composition were investigated. One of the swatches

(dating to 2003) is now water sensitive, whilst the other (dating to 1993) is not. Water sensitivity

appeared to be related to the degree of cross-linking and oxidation of the paint, where the water

sensitive paint (2003) had a more polar and less extensively polymerized network25. Such

difference in the degree of cross-linking might be related to the age difference between the two

paints. This led to the hypothesis that poorly developed and polar polymeric networks are more

likely to be affected by water and other polar solvents. During solvent cleaning, via diffusion and

swelling mechanisms, the dissolution of non-polymerized diacids present both in the bulk film and

on the paint surface may occur, resulting in observable pigment pick-up and surface change.

The insufficient formation of the polymeric network, as well as the migration of polar fractions

comprised of dicarboxylic and hydroxylated fatty acids is also associated with other observed

degradation phenomena, such as the migration and exudation of the paint binder26(Figure 3, left),

as well as the phenomenon of liquefying or dripping paints14,15,27-30 (Figure 3, right).

 Figure 3. Left: liquefying or dripping paint: detail from Harvest (1993) by Otto Piene. Reproduced
30
with permission from Schulz Copyright (2011) ICOM-CC. Centre: exudation of the oil binder on

the paint surface visible as yellow protrusion in the white paint; detail from Lover's Duet (2008) by
26
Ana Tzarev. Reproduced with permission from Bayliss at all Copyright (2016) Elsevier. Right:

cobalt blue dripping paint: detail from Composition (1952) by Jean-Paul Riopelle; Photo: Ida Antonia

Tank Bronken. Reproduced with permission.

Paint exudates and drips have been shown to be generally characterised by a relatively high

content of diacids and hydroxyacids at paint surfaces when compared to the bulk film. This has

been attributed to the fact that although a cross-linked network may form upon curing, a fraction

of triglycerides – possibly containing mono-unsaturated fatty acids, may fail to crosslink to the

wider network and oxidise to form acidic and hydroxylated polar moieties. When these oxidised

species cannot chemically bind with pigments, they are free to migrate to the paint surface, via a
phase-separation mechanism leading to the formation of exudates, drips and tacky surfaces 14,15,26-
29
.

As a lack of polymerization and higher degrees of oxidation of the binder appear to be associated

with several kinds of degradation phenomena in modern oil paints, the film curing process, which

entails crosslinking and the oxidation of triglycerides of polyunsaturated fatty acids, is likely to be

key in determining the establishment of these phenomena

Paint curing

Oil fraction

The curing of a drying oil is an autoxidative process. It is not a thermodynamically spontaneous

process, as ground state triplet oxygen cannot directly add to the singlet state double bonds of

unsaturated fatty acids31. Light and heat provide the high energy required to extract hydrogen

atoms from unsaturated glycerides and form ab initio radicals (R·), and certain metals lower the

energy barrier. In the case of an oil paint layer the formation of R· may be catalysed by pigments

often containing heavy metals and possibly driers, fillers and other additives, which can be

additional sources of metal ions.

Once the radical R· is formed, under ambient oxygen pressure, oxygen can be added to form a

peroxyl radical ROO·. According to classical theory for the autoxidation of lipids, once ROO· is

formed, propagation begins, with ROO· abstracting hydrogens from nearby molecules to form a

relatively stable intermediate hydroperoxide (ROOH) while generating a new radical (R’·) at the

same time32. Hydroperoxides may decompose to alkoxyl radicals (RO·) and OH·. This step is
considered to be the key rate-limiting step33 based on the fact that it is the only propagation step

involving any significant activation energy34.

Termination reactions resulting from the recombination of radicals allow the formation of non-

radical products, such as relatively unstable peroxides, or the relatively stable products of cross-

linking reactions and oxidation 35. When peroxides are formed, these will react further with time,

undergoing scission and forming alcoxyl radicals (RO·). Some of the oxidation products are low

molecular weight and may remain liquid inside the network, or slowly volatilise. Other oxidation

products may further oxidise, ultimately leading to the formation of acidic moieties36.

Cross-linking reactions result in the formation of oligomers, causing an increase in viscosity of the

paint film, until a polymer network is formed, resulting in a rubbery solid paint film. In the earlier

stages of curing, the polymer and oxidation products contain double bonds,36 and it has been

shown that the oligomers formed initially contain an intact number of double bonds37. Overall, the

‘young’ paint layer is relatively macromolecular and non-polar. Unreacted double bonds continue

to react over time38,39 and we hypothesise that at this stage, the reaction pathways leading to

water-sensitivity and other degradation issues may become established.

The literature on oxidation of lipids, mostly focussed around food research, describes the

complex reactions involved in the autoxidation of lipids31,32,38-41. The lipid oxidation kinetics and the

observed reaction products are frequently inconsistent with expected reactions or product

patterns, based on traditional free-radical chain reaction models41. It has been proposed that such

discrepancies can be ascribed to the fact that both ROO· and RO· may undergo other alternative

reaction pathways - in competition with hydrogen abstraction41. A summary of the main reactions

that ROO· and RO· may undergo is shown in Table 1.

Table 1. Summary of the main reactions taking place upon lipid autoxidation 32,38,39,41.
 process ROO· RO· R·

Initiation RH → R·

Addition of O2 R· +O2 → ROO·

Hydrogen ROO· + RH → ROOH + R· RO· + RH → ROH + R·

Abstraction

ROO· + R1OOH → ROOH + R1OO· RO· + R1OOH → ROH + R1OO·

β-Elimination of ROO· → R· + O2
Oxygen

Internal O O + O2 + RH HO O O O R1 R2
R2 R1
rearrangement R R CH
O O
+
R
Addition to double R1 O R R
R1 R1 O OR O2 R1 O OR R1
bonds ROO + RO + R2 R1 R + R2
R1
CH OO
CH R2 CH R2
R2 R2 R2

R1 R1
HC
O O2 OO O

R2 R2
+
RO

(α and) β-scission ROO· + R1OO· → [ROOOOR1] → RO· + ·OOR1 → RO· + O2 + O

·OR1 R1 + R2
H
O
R1 or
R2
O
H + R1
R2

Disproportionation ROO· + R1OO· → [ROOOOR1] → ROOR1 + O2

Recombination R2 RO· + R1O· → ROOR1 R· + R1· → R-R1

OO R1 OH O
2 R1
R2 R1
OOOO R1
R2
+ R1
R2
+ O2
R2

RO· + R1· → ROR1 R· + R1O· → ROR1

R2 R2 O
2 R1 OO 2 R1 O + O2 2 R1 + 2 R3
O
R3 R3 R2 O
R1 + R R1 + RH
R2 R2
 R· + R1OO· → ROOR1

2RO· + O2
2 ROO· → [ROO· O2 ·OR] → or O O
ROOO + O2
R1 + RO R1 + ROH
R2 R2
 ROO· may generate R·, RO·, other peroxides and hydroxyperoxides, as well as non-radical

oxidation products such as epoxides and ketones. RO· may generate R· and non-radical oxidation

products such as alcohols, aldehydes and ketones.

Cross-linking with the formation of a stable bond (R1OR2, R1R2) - which is fundamental to paint

curing - occurs only when R· and RO· radicals add to double bonds and when R· and RO· radicals

recombine (Scheme 1).

Scheme 1. Recombination reactions leading to the formation of stable cross-links

R1O· + R2· → R1OR2

R1· + R2· → R1R2

ROO· may also add to double bonds, resulting in peroxide crosslinks which will be subject to

further reactions (Table 1). It is thus reasonable to suggest that one key factor that determines

the formation of an extensive and relatively non-polar polymeric network may be the result of

the differing chemistries of ROO· and RO·, whose rate of formation and decomposition depends

on several influencing factors, including the paint thickness, the nature of the pigments and

additives present in the paint formulation, the type of oil, and the curing environmental

conditions.

17
 Pigments and additives

It is reported that depending on the environment, the decomposition of ROOH may follow

different pathways (Scheme 2) 32,42

Scheme 2. Possible pathways of decomposition of ROOH 32,42

ROOH → RO· + OH– (reducing metals)

ROOH → ROO· + H+ (oxidizing metals)

ROOH → RO· + ·OH (heat and UV, and through driers)

In the presence of ultraviolet (UV) light and/or through driers (that do not affect the

oxidation/reduction process42), ROOH is quickly converted into RO· + ·OH. As a result, curing

follows a reaction pathway ultimately leading to the formation of a stable paint containing

oxidised species together with a well-established polymeric network (Table 1, Scheme 1). Lead

white containing paints tend not to be water sensitive10,43. Lead based pigments are known to

act as efficient through driers44, which quickly lead to a full consumption of double bonds and

the formation of dicarboxylic acids and a polymerised network. It has been proven that catalysis

takes place when lead dissolves into the paint, and thus the kinetics and efficiency of the curing

process depends on the pigment, the presence of impurities and residues of the pigment

preparation process, and ambient environmental conditions44. Basic lead carbonate has been

18
extensively used as white pigment in oil paints since antiquity, however it was largely substituted

by other white pigments in the early-to-mid-20th century by manufacturers due to toxicity

concerns44. As a result, formulations of modern artists’ and industrial white oil paints are mostly

devoid of lead and now contain titanium and/or zinc oxides.

In an oxidative environment, curing is dominated by the reactivity of peroxyl radicals (Scheme

2). With reference to the reaction schemes shown in Table 1, ROO▪ results in more oxygen

addition in comparison to RO▪ (see " internal rearrangement, addition to double bonds, and

recombination reactions"), thus forming a paint film containing a relatively high proportion of

oxidised compounds and a relatively lower proportion of cross-linked network.

On this basis, it may be hypothesised that in an oxidising environment after the initial stage of

formation of oligomers and the cross-linked network, any remaining unreacted double bonds

may be subject to oxidative degradation, predominantly following the reaction pathway of ROO▪

which leads to the fragmentation of the polymeric network and the formation of non-

crosslinked, relatively low molecular weight polar species. Such a paint is likely to be vulnerable

to the action of water via diffusion, facilitated by both an insufficient degree of crosslinking

coupled with the relative hydrophilicity of the paint film, leading to swelling, solubilisation of

polar compounds and a general vulnerability to mechanical action.

This hypothesis is consistent with observable characteristics of water sensitive paints such as:

they may contain a higher content of extractable dicarboxylic acids and/or oxidised glycerides;

they may contain higher amounts of hydroxylated and acidic moieties covalently bound to the

polymeric network10,25 derived from the formation of cross-linked dicarboxylic acids24.

19
Dicarboxylic acids are end-products of the oxidation of drying oils45 . When using established

analytical methods based on chromatographic techniques, azelaic acid is the most abundant

product of oxidation observed45, deriving from the oxidation of unsaturated fatty acids with an

unsaturation in position 9. In polyunsaturated fatty acids, oxidation may equally occur at other

positions. In these cases, dicarboxylic acids are formed, which still contain double bonds in their

structure. The unreacted double bond may undergo further oxidation or cross-linking and as a

result, a dicarboxylic acid covalently bound to the polymeric network can be formed (Scheme 3).

Scheme 3. Possible pathways of oxidation of linoleic acid leading to the formation of azelaic

acid (1) or dodec-3-enedioic acid (2). Dodec-3-enedioic acid (2) can further oxidise to azelaic acid

(1) or undergo cross-linking. In the figure, cross-linking is depicted as a consequence of the

addition of radical R▪ to the double bond of dodec-3-enedioic acid, followed by recombination

with radical R1▪. The final result is that dodecandioic acid is covalently cross-linked (3).

20
 OH

<ox> <ox>

OH
O OH OH
O
OH O O
(1) (2)
<ox> + R·

OH
O OH
CH OH
O
OH O
R O
(1)
+ R 1·

1
OH R
OH
O
R O
(3)

Another, undocumented but possible pathway of oxidation of the developing polymeric

network may relate to oxidation at the alpha position to carbonyl groups of glycerides and acids.

Although hydrogen abstraction in this position is less energetically favourable than in allylic

positions, it requires less energy than in an internal alkane C-H: dissociation energy of allylic C-H:

350-370 kJ/mol, α to a carbonyl C-H: 390-400 kJ/mol, internal alkane C-H: 410-420 kJ/mol46.

Furthermore, oxidation of methyl or methylene groups α to a carbonyl can be promoted in

specific conditions to give hydroxyl ketones, aldehydes, or carboxylic acid derivatives47. These

reactions require either certain enzymes or oxygen in combination with specific catalysts,

including Mn-based compounds47. Hydrogen abstraction as well as hydroxylation α to a carbonyl

21
might lead, upon further oxidation, to the formation of oxalic acid. Insoluble salts of oxalic acid,

mostly Ca, Cu, and Zn, have extensively been observed in cultural artefacts, including paint

layers48-50, and their formation is commonly believed to be the result of the biological or

chemical degradation of the organic binder49,51,52.

Curing dominated by the reactivity of peroxyl radicals is likely for paint mixtures containing

surface driers (or oxidative driers42), such as Co (II) soaps, or pigments and/or driers based on

oxidising metals (such as Fe(III), Mn(IV), etc.). Actually, paints containing Earth pigments [Fe(III)

and Mn(IV)], chromium green [(Cr(III)], cobalt blue [Co(II)] and ultramarine blue have frequently

been reported as water sensitive10.

Although Co (II) is not an oxidiser, driers based on Co (II)37,42 are classified as primary driers or

oxidative driers. Co-based driers promote the isomerisation of double bonds and the formation

of conjugated systems37. The curing mechanisms of conjugated double bonds are different to

those of fatty acids containing bis-allylic carbons. When conjugated double bonds are present,

the addition of RO▪ and ROO▪ to double bonds is favoured17. Co-based driers are also capable of

catalysing the decomposition of ROOH into RO▪ and ▪OH. In addition, it has been shown that Co

(II) may react with oxygen at the paint-air interface to produce singlet oxygen, which is very

reactive towards double bonds, forming cyclic peroxide structures and hydroperoxides. Hence

the classification of Co (II) based driers (generally sold as Co soaps) as oxidative driers42. One

experiment showed that, after catalysing the formation of oligomeric structures during curing of

ethyl linoleate, in the long term a Co based drier promoted a series of decomposition reactions

which overwhelmed the polymerisation reactions37. Similar phenomena may take place in paints

22
containing Co-based pigments where, after an initial stage in which drying and subsequently

polymerisation has taken place, other reaction pathways become dominant, leading to the

oxidative degradation/fragmentation of the paint film35,37.

Earth pigments [Fe(III) and Mn(IV)] are often associated with a very high level of oxidation10,24. In

particular, in water-sensitive mature oil paint films containing iron-based pigments, the relative

content of azelaic acid is quite high, as well as the relative content of dicarboxylic acids that are

covalently bound to the polymeric network10 (Scheme 3).

With regard to ultramarine blue paints, which are frequently associated with water sensitivity10,

recent studies have shown that with exposure to UV light, ultramarine blue pigment is capable of

photo-catalysing the degradation of oil paints via a free radical process53. Ultramarine blue

containing oil paints are slower to dry than lead white-based paints, and are characterised by

relatively high levels of oxidation products, including oxidised di- and tri-glycerides and

dicarboxylic acids10. Interestingly, ultramarine-containing paints are often associated with

oxalate patinas in Italian paintings from the 15th and 16th centuries54.

Water sensitivity is however, not unequivocally ascribable to paints containing a relatively high

content of dicarboxylic acids, and/or oxidised di- and tri-glycerides. When metal soaps are

formed as the product of reactions between fatty acids and certain cations, the metal might

become an active catalyst, as has been established for lead white44, manganese oxide, and

certain other metals55. In these conditions, oxidative degradation of the polymeric network may

take place, which may not necessarily lead to the formation of free dicarboxylic acids, and may

not therefore be detected using standard chromatographic methods. In addition, pigments and

23
additives containing reactive metals may also form carboxylates via reactions with acidic

moieties produced by hydrolysis and/or oxidation of the drying oil. Studies indicate that metal

soap interactions become an integral part of a cross-linked, ionomer-like network, in which

acidic moieties are covalently bound to the polymeric network and free fatty- and dicarboxylic

acids are coordinated with active metals within a three-dimensional structure21,22,24,56,57. The

relative significance of metal soap interactions vs. covalent crosslinks for the stability of mature

oil films is not yet fully understood. However, metal soap interactions are generally considered

to contribute towards the stability of the paint film, given that metal soaps of alkaline earth and

transition metals are all highly insoluble. Indeed, lead white and zinc white containing paints,

which readily form metal soaps in oil, are almost never water sensitive10. Moreover, it was

shown that paints that drip contain lower amounts of the pigments and extenders that allow the

formation of metal-ionic bridges with the organic moieties, such as those containing lead, zinc,

copper and even calcium28. It is reported that " lack of this anchoring stabilisation leads to

accumulation of polar fractions and results in softening and eventually dripping of the paint" 28.

For many other pigments (such as those containing other metal ions not listed above and

synthetic organic pigments) no general tendencies have been observed. In this case, the same

pigment may or may not show water sensitivity irrespective of the paint brand and age10, which

could be due to the environmental conditions in which the paint films cure and age (see

paragraph External Environment), as well as possible changes in paint formulation, as well as

artist addition and amendments. In fact, the presence of additives, pigment particle size,

underlying paint layers, trace ingredients and unreacted species remaining from formulation

24
processes as well as the presence and type of any applied pigment coating may all contribute to

the dominant reaction pathway(s) of the curing process24,55,58.

Oil type

Traditionally, drying oils such as linseed were used by artists, however modern oil paint

formulations often contain a range of different drying and semi-drying oils 10,24, and in some

cases, even non-drying oils16. The linolenic acid content of these oils varies considerably, which

directly impacts upon drying properties. Linseed oil has a very high content of linolenic acid,

whilst semi-drying oils, such as safflower, soybean and sunflower are mainly composed of

glycerides of oleic and linoleic acids59. Linolenic acid contains three non-conjugated double

bonds, and two bis-allylic carbon atoms. Linoleic acid contains two non-conjugated double

bonds and one bis-allylic carbon, and oleic acid contains one double bond and no bis-allylic

carbon atoms. The presence of double bonds, allylic and/or bis-allylic carbon atoms is directly

related to the reactivity of these fatty acids, and hence the different oils, towards the formation

of alcoxyl and peroxyl radicals.

RO· hydrogen abstraction is very fast32, and less selective than ROO·, as RO· may abstract

hydrogens both at the allylic and bis-allylic positions. Conversely, ROO· can only abstract bis-

allylic hydrogens, and has a half-life several orders of magnitude longer than RO·32. In an

oxidising environment, ROO· dominates the curing of the oil (Scheme 2), and in this case the

limited number of bis-allylic positions of linoleic acid might favour the addition of ROO· to double

bonds in preference to hydrogen abstraction38 thus, favouring oxidative pathways. Furthermore,

the availability of bis-allylic hydrogens may be further reduced by the increasing viscosity of the

25
developing polymeric network, leading to an increased rate of alternative reaction pathways for

ROO▪ radicals (Table 1) during advanced stages of curing. On this basis, it may be expected that a

semi-drying oil may be more prone to the formation of a highly oxidised paint film, and thus

more susceptible to water sensitivity.

External environment

The environment in which the curing of an oil paint takes place is also likely to play an

important role. High relative humidity in conjunction with sulphur dioxide exposure are known to

favour the transformation of magnesium carbonate into soluble epsomite, a known cause of

water sensitivity4. Water activity also strongly affects the rate and pathways of lipid oxidation34

and it has been shown that the exposure of paints to high relative humidity may cause oxidation,

both when the paint is young and also in paints cured over 10 years60. This may be due to the

fact that high relative humidity enhances the mobilisation of catalysts and radicals38. If high

relative humidity may favour oxidation, it is reasonable to hypothesise that curing at high relative

humidity levels might favour the development of water sensitivity. This was supported by in a

recent study, in which Winsor & Newton artists oil colour paints in three selected colours

(French ultramarine, yellow ochre, cadmium yellow) were cured under ambient conditions for six

weeks before being accelerated light aged at elevated relative humidity (70-80%), at 30°C, under

an average of ~3500 lux illumination with the ultraviolet (UV) component filtered out. Samples

became water-sensitive after 2.5 months under these conditions61.

26
 Conclusions

Based on the authors previous research, and other studies presented in the literature, this

paper presents the hypothesis that water sensitivity as well as other degradation phenomena of

modern oil paintings are related to a lack of polymerization and excess oxidation of the oil

binder. As these reactions relate to the oil curing, the paper investigates chemical reactions

known to be involved in the oxidation of lipids. Experimental evidence presented in previous

research, together with a careful review of reactions involved in the oxidation of lipids leads to

the hypothesis that a lack of polymerisation and high degree of oxidation can be linked with

different reaction pathways that involve the evolution of peroxyl and alkoxyl radicals formed

upon curing. We conclude that when the chemistry of peroxyl radicals dominates the reaction

pathways, oxidative decomposition of the paint film overwhelms cross-linking reactions. We

show that; i) the type of oil - and in particular the use of semi-drying oils; ii) the use of oxidising

pigments; iii) the lack of use of through driers - lead pigments largely used in the past have been

disappearing form modern oil paint formulations for health reasons; iv) the environmental

conditions in which the paint cures; can all contribute to the formation of an excess of peroxyl

radicals, ultimately leading to a failure in forming an extensive and relatively non-polar cross-

linked network in favour of extensive oxidation.

Many complexities are involved in this type of research, and several aspects warrant further

investigation. Paintings are in fact significantly more complex than model paints, being multi-

27
layered and often blended systems. The nature, porosity and water affinity of paint underlayers,

the presence/absence of a protective layer of varnish; the presence/absence of a paint frame,

the nature of each paint layer, the use of synthetic organic pigments and the lack of metals

capable of anchoring the formed cross-linked network and polar mobile phases, as well as the

conservation history, all contribute to determining the molecular composition of a painting, and

thus its appearance and condition. Multi-analytical approaches for the study of model paints

must thus be associated with investigations of works of art.

From the methodological point of view, one of the biggest challenges relates to advancing

scientific methods for the detailed molecular characterisation of the insoluble polymerised

fraction of the oil, which still remains difficult/impossible for most molecular techniques. Nuclear

magnetic resonance based techniques together to computational approaches may potentially

offer information about the effects of water and other hydrogen containing moieties in a larger

data set that would be a useful contribution to studies in this context.

AUTHOR INFORMATION

Corresponding Author

* Ilaria Bonaduce, Via Giuseppe Moruzzi, 13, 56124 Pisa. Italy. phone: +39 0502219328, fax: +39

0502220673, email address: [email protected]

Author Contributions

28
The manuscript was written through contributions of all authors. All authors have given approval

to the final version of the manuscript. ‡These authors contributed equally. (match statement to

author names with a symbol)

Funding Sources

The work was performed within the context of the JPI CMOP project: “Cleaning of Modern Oil

Paints” (Heritage Plus Joint Call project 2015-2018).

BIOGRAPHICAL INFORMATION

Ilaria Bonaduce (PhD in Chemical Sciences, University of Pisa, 2006) is Associate Professor in

Analytical Chemistry at the University of Pisa. Her research focuses on the development and

implementation of analytical methods and models to study organic materials in paints and

archaeological polychrome artifacts, and on the characterisation of modifications undergone by

organic materials as an effect of pretreatments, ageing and interaction with other organic and

inorganic materials.

Celia Duce (PhD in Biomaterials, University of Pisa, 2005) is Associate Professor in Physical

Chemistry at the University of Pisa. Her research focuses on the application of calorimetry and

thermoanalytical techniques for the physico-chemical characterization of biochemical systems,

materials and complex matrices such as proteinaceous and lipidic binders with pigment and

additives.

Anna Lluveras-Tenorio (PhD University of Barcelona, 2009; Marie Curie Intra-European

Fellowship, University of Pisa 2010-12) is Assistant Professor in Analytical Chemistry at the

29
University of Pisa. Her research focuses on the development and optimisation of sample

preparation methods and analytical procedures to study the interaction and distribution of

organic and inorganic compounds in microsamples from cultural heritage.

Judith Lee (PhD from the Courtauld Institute of Art, University of London, 2018;. Judith recently

worked as a postdoctoral researcher on CMOP (Cleaning Modern Oil Paints project, 2015-18),

and is currently a Conservation Scientist at Tate supporting the analysis of works of art for the

Conservation Department

Dr Bronwyn Ormsby (PhD in Conservation Science, Northumbria University, 2002) is Principal

Conservation Scientist at Tate, London where she leads the Conservation Science and Preventive

Conservation team. Her research focuses on art material analysis, modern paints, the effects of

conservation treatments of modern and contemporary painted works of art and the

dissemination of research into practice within the Conservation field.

Professor Aviva Burnstock (Ph.D. (1991) in the Conservation of Easel Paintings (1984) is Head of

the Department of Conservation & Technology at the Courtauld Institute of Art, London. She

worked at the Institute for Molecular Physics in Amsterdam, NL (2003-5), and the Scientific

Department of the National Gallery, London (1986-1992) She has published widely in the field of

painting techniques and materials and aspects of conservation practice.

Klaas Jan van den Berg is Senior Conservation Scientist at the Cultural Heritage Agency of the

Netherlands and is Full Professor of Conservation Science (Painted Art) at the Faculty of

Humanities at the University of Amsterdam. His main interest is the study of modern paintings,

30
including historical manufacturing processes of paints, painting techniques, paint degradation

phenomena, chemical analysis of painting materials and conservation approaches.

31
ACKNOWLEDGMENTS
The authors wish to thank Prof Gennaro Pescitelli of the Department of Chemistry and Industrial

Chemistry, University of Pisa, for the useful discussion on radical chemistry.

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