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RESINS IN CONSERVTION:
INTRODUCTION TO THEIR PROPERTIES AND FPPLICTIONS

E. De Witte
Koninklijk Instituut Voor Het Kunstpatrimonium
Jubelpark 1
1040 Drussel
Delgique

1 Introduction

Mankind has always had the need for products to glue broken parts of objects,
to consolidate brittle structures and to protect fragile surfaces. Till the
early thirties, only natural products such as dammar, mastic, beeswax, drying
oils, gum arabic. fish glue, tar, etc. could be used for these purposes.
Nowadays we have a whole series of synthetic resins at the conservators
disposal and if there used to be a problem of finding a product for a certain
application. there are now so many synthetics available that it beccrnes
difficult to make a choice. The best way to make a justified choice is to
have a basic knowledge of the important properties of the range of synthetic
resi ns.

2 Properties

The structure of synthetic resins can best be compared with chains, made by
stringing together an enormous amount of links. The links are called
monomers or 11 structural units 11 . The reaction to make a polymer out of the
monomers is called polymerization. The chemical, and also many physical,
properties are determined by the nature of the monomer. By incorporating two
rnonomers in one polymer chain, it is possible to combine the properties of
both homopolyrners in the same resin. In this way it is possible to obtain
resins with properties which could never have been made by starting with only
one monomer. A well known example is Paraloid B72, a copolymer of methyl
acrylate and ethyl rnethacrylate. The influence of the properties o+ pure
polymethyl acrylate and pure polyethyl methacrylate on the copolymer is given
in Table 1 (1).

P consequence of the chain structure is that in the solid state resins do not
form crystalline structures. The long chains are all mixed up together and
form a knot. This knot formation explains why in most cases lt takes sorne
tjme to dissolve a resjn. The small solvent molecules have to penetrate into
the knot and untwine it, chain by chain. In the case of crosslinked resinsq
such as polyesters and epoxies, the chains are chemically bonded together. So
it is clear that solvent molecules will be able to penetrate in between the
chains and make the resin swell, but will be unable to rernove one chain from
another. There do not exist solvents for cross linked resins. In order to
remove one chain from another, chemical bonds have to be broken and this
implies the destruction of the resin.

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 PMA Copolymer of MA:EMA PEMA
32:68 30:70

Refractive Index 1.479 1.479 1.481 1.485

Solubility in
cold ethanol - - + +
warm ethanol - + + +

Table 1 Comparison of refractive index and solubility

of polymethyl acrylate (PMA), polyethyl meth-
acrylate (PEMA) and two copolymers of methyl
acrylate (MA) and ethyl methacrylate (EMA).

Another property which makes resins different from other compounds is the
molecular weight (MW). For normal organic products the MW is relatively low
< 1,000) and in one product all molecules are identical. Resins, on the
contrary, have very high MW (up to millions) and in the same resin the given
MW is an average value. A number 0f chains are shorter, a number of chains
are longer than the average chain length. An important consequence is that
resins do not have a sharp melting point but a melting index, whose range can
be of the order of 10 to 20 degrees centigrade. Due to this property, resins
can be used as heat sealing materials. By warming up, the shortest chains
will become liquid, while the longest are still solid. The molten chains act
as a solvent, weaken the whole structure and make it tacky. By decreasing the
temperature, the system becomes solid and tack free.

A third important property of resins is the existence of a glass transition

temperature (Tg). In the sDlid phase each resin has a glass-like phase, in
which it is brittle and hard, and a rubber-like phase in which it is softer
and more elastic. The temperature at which the transformation from one phase
into the other takes-place is called the Tg. According to the resin, this
temperature can vary between -50 and +70 degrees centigrade. Ă lthough for
certain applications such as varnishes and adhesives it is very important to
know in which phase a resin is at room temperature, this cannot be seen at
first• sight: in both phases the resin looks like a hard solid. Ă good way to
distinguish which is the room-temperature phase is to crush the resin into a
fine powder and let this stand for some weeks. If the grains stick together,
the resin is above its Tg, if they dont the resin is in its glass-like phase.
The understanding o-f the three basic properties (chain structure, lack of a
fixed MW and the existence of a Tg) allows one to make a reasoned choice for
the use oF a resin in one of the main application fie1ds consolidation,
adhesion, and film forming.

3 Applications

3.1 Consolidation

The consolidation of brittle objects by resins is based on the formation o-F a

network which supports and sticks together the loosened particles. The

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introduction of a synthetic resin as the new supporting material can be
achieved with polymers, prepolymers or monomers.

3.1.1 Consolidation wi€h Polymers

The easiest way to introduce a resin into a porous material is by dissolving

the resin in an appropriate 5olvent and applying this solution to the object.
A typical example is the consolidation of wooden objects with a Paraloid B72
solution in toluene or.xylene.

Although this method is easy to perform there always exists a risk of the
appearance of a chromatographic effect. The small molecules will penetrate
the porous substrate at a faster rate than the long polymer chains and during
evaporation of €he solvent the same eFfect then causes transport of the resin
to the surface. The result is in many cases a consolidated sur+ace layer,
which is in danger of peeling off if the object is exposed to Ltflstable
environmental conditions. Investigations have also shown that the nature of
the solvent and the impregnation conditions are very important (2).

3.1.2 Prepolymers

The chromatographic effect can be decreased by impregnating with prepolymers

such as epoxies and polyesters. The prepolymers can eventually be diluted
with reactive solvents which do not evaporate but are incorporated in the
resin during the polymerization. As both systems lead to cross-linked resins,
care should be taken that no traces of the product are left on the surface o+
the object.

3.1.3 Monomers

Best results are obtained by impregnating the object with monomers and
polymerizing these once they are in their final place. There is no risk for
any chromatographic effect and, because of the very low viscosity of the
monomers, deep impregnations can be achieved.

The initiation of the polymerization depends on the nature of the monomers:

acrylics can be polymerized by X-rays or by adding special initiators (3,4),
silanesand related products react with traces of water. As most monomers are
extremely good solvents, consolidation with monomers is in most cases limited
to non-painted objects. If the system is to be used on polychromed works,
tests have to be made in order to check the resistance of the paint layers
towards the monomers.

3.2 Adhesives

There exists an extensive choice of adhesives on the market, but most

conservation problems can be solved by a limited nLtmber of products.

Although epoxies have been rejected +or a long period because of their
irreversibility and yellowing, there is now a series of resins available
which can safely be Ltsed in conservation.

Baps between non-porous surfaces can be fillecl with viscous or fillecI epoxies

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Porous surfaces can be impregnateci, before glueing, with a liquid reBin. For
complicated compositions fast hardening products can be used and to glue
transparent materials non-yellowing epoxies are available (5). Glued sections
o+ non-porous materials can be undone by swelling the adhesive with dimethyl
formamide or by warming the object to 80-90 degrees centigrade. When using an
epoxy resin care should always be taken to respect very carefully the
proportion of resin/hardener. Even a slight variation will alter the final
properties of the resin.

For the r- epair of stone objects, polyesters are most often used and, in this
instance also, liquids with a range of viscosity, and pastes, are available.

Before using a polyester, a test should always be made in order to control the
reactivity of the resin. The polymerization reaction involves an increase in
temperature, which in its turn accelerates the reaction. So care should be
taken to prepare quantities which can be useci in 5-10 minutes.

During the polymerization polyesters are sensitive to water, which means that
high relative humidities have to be avoided.

Organic solutions of polyvinyl acetate (PV) can only be used in a very

restricted number of cases. In order to obtain a sufficiently high
concentration, a PVA resin with relatively low MW has to be used. At room
temperatt.tre such a PVA is above its Tg which leads to the real danger that
after some time the glue will start to flow under the weight of the object. An
excellent way to obtain a free-flowing liquid with a high MW resin is to
prepare a dispersion in water. The viscosity is then no longer determined by
the length of the polymer chains, but by the amount and the size of the
polymer spheres. The main problem encountered with these kinds of glues is
that they are, in most cases, too good adhesives. Care should be taken that
the new bond is not stronger than the original material, in order to avoid new
ciamage when tensions occur in the object.

recent comparative stLtdy (6) has shown that there exists a wide range of
commercial white glues but that not all of them have the same properties.

3.3 Varnishes

The varnishing of a painted surface has two purposes: to protect against

slight mechanical damage and to make the colours Iook more saturated. The
chemical stability can easily be tested and calculated, but the judgement of
the optical gualities is more subjective and depencis on the nature of the
object.

it this moment five synthetic varnishes are currently used in restoration.

Table 2 gives their most important properties.

ccording to the restorers of the Koninklijk Institiiut Voor Het Kunstpatri-

monium, Ketone N gives the best optical results on old oil paintings.
Unfortunately this varnish not only shows slight yellowing or ageing, but its
solubility also decreases considerably. Although the coating can always be
removed by powcierinq off, tests have shown that the solubility can be
increased by protecting a Ketone N varnish with a coat of Paraloid B72. As
the optical effect of a two-component system is determined by the underlying
layer (7) the B72 has no optical influence on the painting.

Optical Chemical Solvent

Properties Stability

Ketone N ++ - white spirit

Paraloid B72 + ++ toluene, xylene

Paraloid H7 + + white spirit

Mowilith 50 +- ++ toluene

Ketone N + B72 ++ + white spirit/toluene

Table 2. Key properties of five varnishes currently used in

restorat i on.

When the restorer is satis+ied with the appearance o+ an acrylic resin and the
painting is insensitive to toluene, Paraloid 972 would be the preferred
varnish. The stability of this resin has been proved over and over again anci
the resin is even used as a reference material in Fellers classification of
stability (8). Acrylics like n- or iso- buty .1 methacrylate have the advantage
that they are soluble in white spirit, but their stability is much lower than
that o+ B72. In spite of the information available in plenty on this subject,
a recent investigation (9) has shown that all commercial varnishes in Belgium
are based ori these less stable products, so restorers are still thrown ori
their own resources to prepare the B72 varnish.

4 Conclusion

very important point in selecting a synthetic resin for conservation

purposes is to choose a resin +or which the use+ul properties have beeri
thoroughly tested. P literature search on analogue applications can be very
use+ul although the fact that a resin has been used fcir a certain applicatiori
is not a guarantee that the long-term results are excellent. Information on
erroneous applications is indeed scarce.

When reporting the application o+ a synthetic resin it is absolutely necessary

to give an exact identification or at least the complete trade name. Only in
this way will an evaluation of the results obtalned be possible.

When artificial ageing is carried out, it uould be most advisable tci use the
reference materials proposed by Feller (8). It is the aim o+ the ICOM-
Conservation Committee Working Group, Coatings: Evaluation and
Characterization, to collect the use+ul in+ormation on synthetics, (such as
chemical composition, ageing phenomena, substitution products etc) arid to keep
these at the disposal o+ conservators.

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