S04 METHODS AND APPROACHES FOR THE TREATMENT AND CARE OF EASEl PAINTINGS AQUEOUS METHODS FOR THE

AQUEOUS METHODS FOR THE CLEANING OF PAINTINGS S05

Table 30.1 Common buffers, pK.s, and ranges for buffering effects 30.2.3 Chelators
(Note that citrate and phosphate Ions are also chelating agents) Chelating materials are widely used in aqueous preparations for cleaning fine art surfaces. They function
as aids in dissociating relatively low-solubility-product saltli present in the fonll of soils or deterioration
Buffer range pK. Buffer
products from the paints themselves. (The 'p' notation indicates a logarithmic function; the higher the
2.2-6.5 3.13 citrate (pK1)
.
pK number, the more insoluble a salt is in solution.) Chelators can also have an 'anti-biological' or
preservative effect. However, it is the dissociative function that is most often exploited in tenllS of clean-
3.0-6.2 4.76 citrate (pK2)
ing effects. Citric acid is used most often, but EDTA, HEDTA, DPTA, and NTA can also be effective.
3.6-5.6 4.76 acetate Their adoption follows from the specific fonnation constants required and the solubility products of the
materials to be solubilized. (Note that HEDTA and NTA are suspected human carcinogens and should
6.0-8.0 6.35 carbonate (pK1) be used with appropriate safeguards.)
Chelators generally work because they are water-soluble molecules that can attract and bind metal
5.5- 7.2 6.40 citrate (pK3)
ions but not precipitate in the process; they remain in solution even when associated or complexed with
5.8- 8.0 7.20 phosphate (pK2) the metal ion. Chelators are usually molecules that carry very polar or multiple ionizable b'TOUPS on their
structure. Citrate, a good example of a chelator, contains three ionizable carboh"'Ylic acid b'TOUPS and an
7.0-8.3 7.76 triethanolamine (TEA)
additional OH group. When at least two of the ionizable acid b'TOUPS are above their pKas (i.e. when
7.5- 9.0 8.06 Trizma (Tris) they arc fully ionized) both can attract the oppositely charged ion and hold on to it. The OH group
also helps attract and hold metals by sharing un-bonded electrons on the Oh"'Ygen in that group with the
8.5--10.2 9.23 borate (pK1) metal. The ability of a molecule such as citric acid to act as a chelator is pH dependent; citric acid as the
free acid is virtually uncharged in solution (pH 2), but as the pH rises above the pKJ of each of the three
9.5- 11.1 10.33 carbonate (pK2)
acid b'TOUPS present on the molecule (3.13, 4.7(), 6.4), the force of attraction possible with metal ions
increases dramatically. The force of attraction is usually expressed with a logarithmic 'p' number, the
pKf for the metal ion and the chelator. The pKc's reach a maximum when all three add groups on citrate
arc fully ionized (in other words above a pH of6.4). Every chelator is different; each has different pKas
separation and adsorption on to oil paint surf.1ces. These non - ionics arc generally used in dilute ionic
and abilities to bind metals, but they all act in a similar f.lshion. Binding force is dependent on pH and
strength preparations and in the presence of mono-valent ions such as Na", K t- , NH .. t , and triethanolate
ion to avoid any substantial cloud point depression from divalent ions (SO;~, COJ-~ (Wolbers, 2008). chelate structure (Wolbers, 2000: 109).
The pK( for a given metal ion for a chelator must be larger (by an order of magnitude or so) than
Higher HLB surfactants (anionic surfactantli such as sodium lauryl sulphate (SLS, sodium dodecyl sul-
the pKsp of the concomitant metal salt for complexation (and dissociation of the salt) to take place.
phate, SDS) and Vulpex) have been used by some conservators in the past. However, these materials
CaSO 4 for example is only sparingly soluble in water; itli pK.,. is 5.04; for each mole of CaSO~ , only
tend to be rather strong solubilizers of hydrophobic paint film constituents (including the oil-binding
1 x 10- 5 M will dilisociate at standard temperature and pressure. The pK,,, is a logarithmic notation; as
materials themselves) and tend [0 be the strongest water/oil type emulsion fornlers. Hence they should
the number increases, the solubility of a salt at standard temperature and prL'Ssure goes down. Each unit
probably be avoided; prolonged contact with concerted SLS will emulsify a water phase into artists' oil
increase means therefore a decrease in solubility by a f.lctor ofl0. Using a similar 10g:lrithmic notation,
pain to;. Artists' oil paint~ are not impervious to water; they exhibit pronounced swelling and dissolution
the affinity of a chelator for a metal ion increases ao; the pK f goes up. For each unit increase in the pK(,
effects when exposed to water-miscible solvent additions to aqueous preparations with strong or high
the strength of binding to the chelator goes up by a factor of 1O. For chelation to take place, the Kfmust
HLB surfactants and at elevated ionic strengths and pHs.
Effective surf.lctant concentrations are deternlined by their CMCs (critical micelle concentrations, be larger than the K." For CaSO4 to be solubilized by a chelator (in other words to move the reactions
towards complex fonllation or to the right, below) Kf for citrate/ calcium must be greater than the K1fI
the concentration at which they begin to fornl micelles or solubilize materials), which vary with solution
conditions (temperature, ion concentration, pH). Only a slight excess of surfactant beyond the CMC is of CaS 0 , :
needed for effective cleaning or solubilization to take place (5X the CMC). Surfactant HLBs are gener..
ally kept as low as nceded (in the range of 12-20) (Wolbcrs, 2008). K.. K,
The bile acid, deoh"'Ycholic acid, and the natural resin acids (abietic and alueritic acids) are known as CaS04 .. ~ Ca+! + S04 ~' ~ .. Ca" Citrate (+ SO; ')
'affinity' surfactants (Wolbers, 2000: 39), i.e. surf.1ctants that have been adopted because they can often
solubilize specific substrate materials. Deoh"'Ycholic acid tends to bind specifically free fatty acids, and the The challenge is to select a chelator that can help dissociate a soil salt (surpa~s it~ pKsp, but not be so
latter two resin acids have been used to solubilize other di- and tri-terpenoid materials, based on their strong as to dissociate pigments or other materials in paint films that must be retained). Table 30.2 pro-
stereo-specificity for these materials. Free fatty acids or their metal salts often comprise the weathering vides typical pK( values for fully ionized common chelators.
materials on oil paint surfaces; degraded di- and tri-terpenoids are often associated with natural resin
varnishes, which have been applied to oil paintings for centuries as varnishes.
.
Table 30.3 provides pK values for common white pigments for comparison .
506 METHODS AND APPROACHES FOR THE TREATMENT AND CARE OF EASEL PAINTINGS AQUEOUS METHODS FOR THE CLEANING OF PAINTINGS 507

Table 30.2 Common chelators and pK, for selected metal Ions (Wolbers, 2008) Antimony oxide Sb,o, 5.22

EDTA EGTA HEDTA NTA DTPA Cltrate Zinc white ZnO 7.64

Ag(l) 7.32 6.88 6.71 5.16 7.1 Aluminium stearate AI(C 18 H"O,), insol.

Ca(lI) 10.96 11 .00 8.14 6.41 10.9 4.68 Aluminium hydrate AI(OH), 32.9

Cd(lI) 16.46 16.70 13.6 9.54 19.3 3.98 Gypsum CaSO:2H,O 5.04

Co(lI) 16.31 12.50 14.4 10.38 19.3 4.8 Talc 3MgO*4SiO,*H,O 3.7 (MgO)

Cr(lIl) 23.40 >10 Chalk CaCO, 8.54

Cu(lI) 18.80 17.88 17.55 12.96 21.5 4.35 Baryte BaSO, 9.96

Fe(lI) 14.33 11.92 12.2 8.84 16.0 3.08 Barium carbonate BaSO, 8.29

Fe(lll) 25 .1 20.5 19.8 15.87 27.9 12.5 Lead stearate Pb(C 18 H"O,), 5.26

Hg(I) 21.8 23.12 20.1 14.6 26.7

li(I) 2.79 1.17 2.51

Mg(lI) 8.69 5.21 7.0 5.46 9.0 3.29 30.2.4 Enzymes

Mn(lI) 10.7 7.44 15.6 3.67 Enzymes can be used as adjunct aqueous materials [0 facilitate the breakdown and solubilization of
14.04 12.3
~c1ected biopolymers associated with coating, consolidation, and retouching materials. Enzymes can
Na(l) 1.66 1.38 2.15 be selected to hydrolyse or breakdown the primary ester linkages in drying oils (lipases), the glycosidic
linkages in starches (amylase), and the peptide bonds in prmeinaceous materials (proteases) to facilitate
Ni(lI) 8.62 13.55 17.0 11.54 20.2 5.11
removal from painting supports or surf.lces.
Pb(lI) 18.04 14.71 15.5 11.39 18.9 6.50 Enzymes arc catalysts: they can increase the speed of chemical reactions without undergoing any
pem13nem chemical change themselves. They arc neither used up in the reaction nor do they appear as
Sn(lI) 18.3 23 .85 reaction products. They f.1cilitate reactions that arc already favoured thennodynamically by lowering the
TI(lll) 22.5 18.0 activation energy required for the catalysed reaction to go forwards.
All known enzymes are proteins. They are high molecular weight compounds made up principally
of chains of amino acids linked together by peptide bonds. Their molecular weights range from t a,ono
to 2.000.000 D.ltons in size (Wolbers, 2000: 128).
Table 30.3 pK,. values for common white pigments (Wolbers, 2008) One of the properties of enzymes that make them attractive as reagents is the specificity they exhibit
relative to the reactions they catalyse. A few enzymes exhibit absolute specificity; they will catalyse
Pigment Formula pKsp only onc particular reaction. Other enzymes will be specific for a particular type of chemical bond or
functional group. There are four types of specificity associated with enzyme catalysed reactions: absolute
Titanium calcium white TiO" CaSO, insoI., 5.04
specificity (the enzyme will catalyse only onc reaction), group specificity (the enzyme will act only on
Titanium dioxide (rutile) no, InsoI. molecules that have specific functional groups), linkage specificity (the enzyme wi1l act on a particular
type of chemical bond regardless of the rest of the molecular structure), and stereo-chemical specificity
Titanium barium white TiO,,8aSO, Insol.,9.96 (the enzyme will act on a particular steric or optical isomer).
White lead (basic sulphate) PbSO: PbO 7.79, insol. Enzymes can be classified by the kind of chemical reaction catalysed. Hydrolases, for instance, are
the enzymes used most often for conservation cleaning purposes. They catalyse the addition or removal
White lead (basic carbonate) PbCO,*Pb(OH), 13.13, 14.93 of water. They include: esterases (e.g. lipase), carbohydrases (e.g. amylase or pul1ulanase), nucleases,
deaminases, amidases, and proteases (e.g. trypsin or pepsin). Other reactions could be used to modify
lithopone ZnS, BaSO, 23.8,9.96
and help solubilize other materials. Other broad classes of enzymes include: hydrases (which catalyse