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Review 399

Summary: Synthetic resins have been extensively employed in the conservation of cultural heritage literature claiming
by artists in their works of art, e.g. as paint binders, or by that microorganisms are capable of degrading synthetic
conservators for conservation treatments, e.g. as stone resins. This paper reviews the researches on the biodeteriora-
consolidants and protectives. It is generally thought that tion of synthetic resins used in the conservation of cultural
synthetic resins are less prone to chemical, physical and heritage, including stone, painting and textile materials,
biological deterioration than other organic products but there carried out in the last fifty years.
are many articles in the scientific literature and some reports

The Biodeterioration of Synthetic Resins Used in


Conservation
Francesca Cappitelli,* Elisabetta Zanardini, Claudia Sorlini
Department of Food Science and Microbiology, Section of MAAE, Agricultural Faculty, University of Milan, Via Celoria 2, 20133
Milan, Italy
Fax: þ39 02 50316694; E-mail: francesca.cappitelli@unimi.it

Received: September 13, 2003; Revised: December 22, 2003; Accepted: January 7, 2004; DOI: 10.1002/mabi.200300055
Keywords: biodegradable; biodeterioration; conservation; microbial attack; resins

Introduction incidences of biological deterioration can occur.[17] The


manufacturing conditions generally prevent microbiologi-
The conservation of cultural heritage is becoming a more cal growth but it is sometimes possible to encounter a
and more important issue to be addressed. A fundamental biological contamination especially with microbial spores,
aspect of conservation is to find the causes and devise stra- which can germinate under favourable conditions. The
tegies to reduce the rate of deterioration of cultural heritage. main effects of the microbiological growth, and conse-
Biodeterioration is any irreversible alteration that implies quently enzyme production, are changes in the viscosity, pH
changes of the material properties caused by microorga- and colour of polymer emulsions and the production of
nisms and/or organisms belonging to different systematic odour and gas in the environment. In order to prevent bio-
groups.[1] Biodegradable materials are those which, because logical growth it is suggested to check water and raw mater-
of their chemical structure, are susceptible to being assimi- ials, improve plant design and hygiene and, finally, use a
lated by microorganisms, such as fungi and bacteria. Bio- broad spectrum biocide.
degradable materials can be either organic, both natural and Different methods can be employed for testing the bio-
synthetic compounds, or inorganic. Natural polymers are degradability of synthetic resins.[18] The current standard
easily subjected to biodeterioration. For example, the de- methods for evaluating the resistance of synthetic resins to
gradation of cellulose has been widely reviewed.[2–4] microorganisms are the ASTM G21-96(2002) ‘‘Standard
Millions of tons of synthetic resins, which are used as Practice for Determining Resistance of Synthetic Poly-
adhesives, binders, coatings, inks, fabrics, etc., are produced meric Materials to Fungi’’ and the ASTM G29-96(2002)
worldwide every year. Synthetic resins have been used by ‘‘Standard Practice for Determining Algal Resistance of
artists in their works of art, e.g. as binders, or by conserv- Plastic Films’’. The first practice covers the determination
ators for conservation treatments, e.g. as consolidants and of the effect of fungi on the properties of synthetic poly-
protectives. It is generally thought that synthetic resins are meric materials. Changes are determined with visual, opti-
less prone to chemical, physical and biological deteriora- cal and electronic observations and measuring mechanical
tion than other organic products but there are many articles and electrical properties. The latter practice covers the
in the scientific literature[5–16] and some reports in the con- determination of the susceptibility of plastic films to the
servation of cultural heritage literature claiming that micro- attachment and proliferation of surface-growing algae.
organisms are capable of degrading synthetic resins. As early as the fifties, some experiments on the biodeter-
Even during the manufacture of polymers, especially ioration of poly(vinyl acetate) resins were reported by the
when dealing with polymer emulsions (aqueous medium), Istituto Centrale del Restauro, Rome. The solid tested

Macromol. Biosci. 2004, 4, 399–406 DOI: 10.1002/mabi.200300055 ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
400 F. Cappitelli, E. Zanardini, C. Sorlini

products were Vinavil K 40, Vinavil K 50, Vinavil K 60, with Vinavil was always present but not as conspicuous as
Vinavil K 70 and Vinavil K 90 (see Table 1 for the supplying in media supplemented with glucose and was characterised
companies).[19] The tests were carried out as follows: a by localised colonies. No growth was ascertained in the
mineral solution, which did not provide any source of negative controls. The penetration of the hyphae in the solid
carbon, was used as such and supplemented either with resins was demonstrated by means of optical observations.
chips of Vinavil or with glucose. After the cultural media
were prepared, they were sterilised in order to kill all the
alive microbes. Once ready, the media were poured into Materials and Objects
non-aseptic spring water, mineral solution (incubation tem-
Stone
perature 19–20 8C), and garden soil (incubation tempera-
ture 27 8C). After one month of incubation, the isolated The main aims of using synthetic polymers in the con-
strains were all identified as mycetes, belonging to the servation of stone are stabilisation and protection. A good
genera Scopulariopsis, Tricotecium, Fusidium and Poecyl- example are epoxy resins that, injected into cracked, crum-
lomices. The growth was already visible after one week bling, concrete wharfs, bridges, and buildings, can rehabi-
but it was considered at its maximum after one month. litate these structures to provide many additional years of
The growth intensity showed to be different depending on service.[20]
the various genera but also among different strains of the In order to prevent the weathering of archaeological
same genera. The microbial growth in mineral media added stone remains in the Roman town of Luni (Liguria, North of

Francesca Cappitelli is a researcher at the University of Milan, where she carries out research on the
bioremediation and biodeterioration of cultural heritage within the European funded project
BIOBRUSH (MIUR fellowship ‘‘Rientro dei Cervelli’’). She received her PhD in Conservation at the
Tate Gallery (RCA/V&A Conservation course) in London in 2002 with a dissertation on the chemical
characterisation of paint binders in the 20th century art. She worked at the Victoria & Albert Museum,
London, and at the Art Collector’s Museum, Milan, and collaborated with the Kunsthistorisches
Museum, Vienna. She is responsible for the topic of biodeterioration within the ICOM-Committee for
Conservation, Modern Materials and Contemporary Art Group.

Elisabetta Zanardini studied biology at the University of Milan. Her PhD in ‘‘Chemistry, biochemistry
and ecology of pesticides’’ was carried out in the Department of Food Science and Microbiology at the
Agricultural Faculty, Milan. In March 2000 she obtained the doctorate degree and from July 2000 she
held a position of researcher at the same University. Since 2000 she is member of a national commission
of Ministry of Cultural Heritage that produces documents as normative and recommendations in the
field of biodeterioration of stonework and is also a member of Italian Society of Microbiology. She
teaches general and applied microbiology at the Science Faculty (Como, Italy) and biotechnology
applied to the conservation of cultural heritage at the Agricultural Faculty (Milan). Her researches are
generally based on microbial ecology and environmental microbiology, in particular on the biodeter-
ioration of artworks and the biotechnology applied to the cultural heritage together with environmental
biotechnologies (European project BIOBRUSH).

Claudia Sorlini is full Professor of Agricultural Microbiology and Head of the Department of Food
Science and Microbiology, Agricultural Faculty, Milan. She teaches Agricultural Microbiology (Agri-
cultural Science and Technology Course) and Microbiology (Crop Biotechnology Course). Her main
interests are microbial biodiversity in different ecosystems, biodegradation of xenotic compounds,
environmental biotechnology (soil bioremediation, wastewater treatment, anaerobic digestion, compo-
sting process), biotechnology applied to the study of biodeterioration and conservation of works of art
and the effect of genetically modified plants and food on microbial population both of the rizosphere and
the gastro-intestinal tract respectively. In addition, she is the coordinator of the master ‘‘Monitoring and
evaluation of genes and transgenes in food and environment matrices’’, editor in chief of the trimestral
journal Annals of Microbiology, president of the Italian Society of Agriculture, Food and Environment
Microbiology, member of the Scientific and Technique Council of the experts for Agriculture and Food
Policy, president of a committee of the Environmental Ministry for the ‘‘Elaboration of guidelines for the
genetically modified environmental risk assessment’’, member of a national commission of Ministry of
Cultural Heritage that produces documents as normative and recommendations in the field of
biodeterioration of stonework. She is author of more than 200 papers.

Macromol. Biosci. 2004, 4, 399–406 www.mbs-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
The Biodeterioration of Synthetic Resins Used in Conservation 401

Table 1. Names of the resins or synthetic resin-based products in the cited conservation literature. The chemical class of each resin from
the literature as well as the supplying company at the time of the investigation are reported.

Name Chemical class Company (at the time of the investigation) References

A2/1028 Alkyd resin Croda Resins 33


Acrylic Acrylic resin Kalon 33
Acryloid F-10 Acrylic resin Rohm and Haas 28; 39
AYAA Polyvinyl resin Union Carbide 28
AYAC Polyvinyl resin Union Carbide 28
AYAF Polyvinyl resin Union Carbide 28
AYAT Polyvinyl resin Union Carbide 28
Beva 371 Keton resin Lascaux Restauro 39
Calaton CA Soluble nylon Imperial Chemical Industries 39
Conservare H Silicone-based resin ProSoCo 28
Conservare H40 Silicone-based resin ProSoCo 28
Conservare OH Silicone-based resin ProSoCo 28
Crodakyd 444w Alkyd resin Croda Resins 33
Crodakyd 826w Alkyd resin Croda Resins 33
Crodakyd 850w Alkyd resin Croda Resins 33
Emulsion A Poly(vinyl acetate) resin Vinamul 33
Emulsion B Poly(vinyl acetate) resin Vinamul 33
Emulsion C Poly(vinyl acetate) resin Vinamul 33
Emulsion D Poly(vinyl acetate) resin Vinamul 33
Emulsion E Poly(vinyl acetate) resin Vinamul 33
Emulsion F Acrylic resin Vinamul 33
Emulsion G Acrylic-styrene resin Vinamul 33
EP 2101 Epoxy resin ? 27
Epidian 5 Epoxy resin ? (Polish product) 24
Fomblin Y Met Perfluoropolyether ? 27
Imron 192S Polyimide Dupont 28
Klucel E Cellulose derivative ? 32
Klucel G Cellulose derivate Lascaux Restauro 39
Lascaux 360 HV Acrylic resin Lascaux Restauro 39
Long oil alkyd Alkyd resin Kalon 33
Mowilith 20 Poly(vinyl acetate) resin ? 32
Mowiol 4-98 Poly(vinyl acetate) resin ? 32
Mowital B-20-H Polyvinyl resin American Hoeschst 28
Mowilith DM 5 Acrylic-vinyl acetate resin Hoeschst 32; 39
Mowilith DMC2 Copolymer of vinyl acetate and Hoeschst 39
maleic acid dibutyl ester
Paraloid B72 (formerly Acrylic resin Rohm and Haas 23; 27; 28; 32; 39
called Acryloid B72)
Plastyrol s99x Alkyd-styrene resin Croda Resins 33
Plastyrol t35w Alkyd-toluene resin Croda Resins 33
Plexisol P-550 Acrylic resin Lascaux Restauro 39
Plextol B-500 Acrylic resin Lascaux Restauro 39
Primal AC33 Acrylic resin Rohm and Haas 23; 32
PVA Poly(vinyl acetate) resin Spectrum Oil Colours 33
resin E0057 Acrylic-siliconic resin Raccanello, Padua 21
resin solution 11309 Silicone resin Rhône-Poulenc 29
Rhoplex AC-234 Acrylic resin Rohm and Haas 28
Silicone 1048 Silicone-based resin General Electric 28
Silirain 50 Silane resin ? 27
Sobral 1241 ML 70 Alkyd resin Scott Bader 33
Styrene acrylic Styrene acrylic resin Kalon 33
Synolac 28w Alkyd resin Cray Valley 33
Synolac 60w Alkyd resin Cray Valley 33
Tegosivin HL100 Siloxane derivative Goldschmidt 27
Tegovakon V Silicone-based resin Goldschmidt 28
Texicryl 13-031 Acrylic resin Scott Bader 33
Thixotropic alkyd Alkyd resin Kalon 33
Tylose MH300 Cellulose derivative Hoeschst 39
Vilkyd 211 Alkyd resin Spectrum Oil Colours 33
Vilkyd 270 Alkyd resin Spectrum Oil Colours 33
Vinavil K 40 Poly(vinyl acetate) resin Società Rhodiatoce (Montecatini group) 19
Vinavil K 50 Poly(vinyl acetate) resin Società Rhodiatoce (Montecatini group) 19
Vinavil K 60 Poly(vinyl acetate) resin Società Rhodiatoce (Montecatini group) 19
Vinavil K 70 Poly(vinyl acetate) resin Società Rhodiatoce (Montecatini group) 19
Vinavil K 90 Poly(vinyl acetate) resin Società Rhodiatoce (Montecatini group) 19
Wacker 290L Siloxane derivative Wacker? 27
XC 41 Epoxy resin Ciba-Geigy 21

Macromol. Biosci. 2004, 4, 399–406 www.mbs-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
402 F. Cappitelli, E. Zanardini, C. Sorlini

Italy), two synthetic resins, the epoxy resin XC 41 and the cemented with Epidian 5. The material tests were brushed
acrylic-siliconic resin E0057, were employed to cover with a suspension of fungi and algae growing on stones in
archaeological areas. According to the manufacturers, these natural conditions. Fungi were able to grow on the speci-
conservation treatments are not only able to prevent deter- mens but not the algae. The classification was performed
ioration by atmospheric pollutants but also to avoid micro- after seven weeks from the inoculation and the predominant
bial growth. Before the employment of the resins the floor species was Aspergillus fumigatus. However, it was not
and columns of a house were covered with a thick film of clear if the epoxy resins or the associated products were
green algae. Although for some months after the treatment food for the fungi. In fact, during the saturation of the stones
the microbial growth was prevented, algal colonies were the hardener that is not bound migrates to the surface of the
then detected. Thus, some biological samples were taken to stone. It must be noted that this was not the first time that it
identify the algae and test their ability of growing on plastic was inferred that the degradation of synthetic polymer-
materials.[21] The green alga was identified as Stichococcus based products may be related not only to the breakdown of
bacillaris. Tomaselli et al. in their study on the biodiversity the polymer but also to other compounds in the formulation.
of photosynthetic microorganisms dwelling on stone monu- It has been reported, in the case of plasticised polyvinyl
ments claimed that the most widespread chlorophyta are chloride, that the plasticisers, which are an easier available
Stichococcus, in particular the species S. bacillaris.[22] In source of carbon rather than the polymer, were attacked
the experiment by Favali, the alga was inoculated on a by microorganisms.[25] In addition, also impurities and
mineral medium containing sucrose and on Petri dishes the residual monomers, as acrylic acid both under anaero-
whose bottom was covered with the same resins used for the bic and aerobic conditions, can support the growth of
conservation treatments. Using traditional cultural methods, the microbes.[26]
light microscopy, scanning and transmission electron Salvadori and Nugari screened five synthetic resins
microscopy, a conspicuous growth on agar-sucrose, sug- commonly used in the treatments of monuments, Silirain
gesting a mixotrophic metabolism, and agar containing 50, Paraloid B72, EP 2101, Fomblin Y Met and Tegosivin
only mineral salts was reported. In addition, it was demon- HL100 dissolved, depending on their solubility, in trichloro-
strated that the algae can survive on plastic films for several ethane, isopropanol, toluene, trichlorotrifluoroethane and
days. The authors suggested that the presence of the algae in hydrocarbons. The resins were put into contact with bio-
situ is due to the fact that they were able to find mineral salts logically active mud. EP 2101, Fomblin Y Met were the
either through small cracks on the plastic films or due to the only products to be resistant to the microbial attack.[27]
deposition of mineral salts caused by the wind. However, it was not proved whether the resistance was due
In another research, the resistance to biodeterioration of to the polymer or to the solvent employed. In addition,
two acrylics, Paraloid B72, which is the most used synthetic Carrara marble specimens and Lecce limestone, treated by
resin-based product in conservation, and Primal AC33, was capillary rise with Tegosivin HL100 and Wacker 290L,
investigated using the soil burial test and the agar plate were partly subjected to soil burial test in accordance to
count.[23] The deterioration was evaluated by measuring the the British standard 6058 and partly exposed to artificial
weight loss. The microorganisms chosen for the inocula weathering in a chamber at 28 8C and 95% relative humidity
were Aspergillus fumigatus, Aspergillus niger, Chaetomium for one month. The growth was assessed with visual and
globosum, Curvularia sp., Trichoderma sp., Ulocladium optical observations, the water repellence by contact angle
atrum, Ulocladium chartarum, Alternaria alternata, and the capillary absorption by the Normal 11/82 method.
Aspergillus flavus, Myxotrichum deflexum, Stachybotrys Microbial growth on stone specimens subjected to burial
atra, Aspergillus terreus, Curvularia sp., and Penicillium test was difficult to determine as soil particles interfered
funiculosum. The authors claimed that, as there was no with the observations and measurements whereas the growth
significant difference between the weight loss of the inocu- was evident in the samples aged in the artificial chamber and
lated resins and the controls, the acrylics did not provide a almost the same for each different specimens and resins.
carbon source for the microbes. However, they concluded The microbes isolated were fungi identified as Alternaria
that the fungal growth interfered with the structural pro- alternaria, Alternaria sp., Cladosporium cladosporoides,
perties of the polymers due to the modification of the water Myrothecium verrucaria, Trichothecium roseum, and
affinity. Ulocladium atrum. Regarding physical measurements,
Domaslowski and Strzelczyk reported that stone objects there was no significant difference between the treated
consolidated with epoxy resins or conserved with epoxy- specimens and the controls with the only exception being
based mortars are sometimes susceptible to microbial Wacker 290L under soil burial test where a slight reduc-
deterioration.[24] The stone specimens were limestone from tion of both water repellence and protective ability was
the Pińczów quarry and sandstone from the Nietulisko observed.
quarry that were soaked in the epoxy resin Epidian 5. The Koestler and Santoro selected six fungi, belonging
hardener used for the stone specimens was the Polish to the genera Penicillium, Fusarium, Cladosporium and
product Z-1. Mortars were prepared from different fillers Aspergillus, and inoculated them on Acryloid B72, Acryloid

Macromol. Biosci. 2004, 4, 399–406 www.mbs-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
The Biodeterioration of Synthetic Resins Used in Conservation 403

F-10, Rhoplex AC-234, AYAA, AYAC, AYAF, AYAT, Mowilith 20, and Mowiol 4-98. In the case of fungal cul-
Mowital B-20-H, Conservare H, Conservare H40, Conser- tures, the acid excretion was also investigated after 13 d,
vare OH, Silicone 1048, Tegovakon V, and Imron 192S.[28] measuring the pH and analysing organic acid formation,
Visual assessment procedures were carried out every week mainly citric and acetic acid, by high performance liquid
until the 35th day. The biodeterioration effects were evalu- chromatography. A small pH shift was observed with Primal
ated with weight loss measurements and Fourier transform AC33 and Klucel E whereas Mowilith-types produced
infrared spectroscopy. However, the latter gave inconclu- significant decreases of pH values, the maximum reduction
sive results. The least susceptible to biodeterioration were being observed for Mowilith 4-98.
Rhoplex AC-234, Tegovakon V, and AYAA, the most affec- Cappitelli et al. studied the biodeterioration of a large
ted were AYAC, Conservare H40, Acryloid F-10, and Imron number of synthetic resins in housepaints, Synolac 28w,
192S. The results suggested that no polymer class behaved Synolac 60w, A2/1028, Crodakyd 444w, Crodakyd 826w,
in a uniform manner when subjected to fungal attack. The Crodakyd 850w, Plastyrol s99x, Plastyrol t35w, Acrylic,
authors were not certain of the presence of biocides in Long oil alkyd, Styrene acrylic, Thixotropic alkyd, Sobral
the product formulations that might have been the cause of 1241 ML 70, Texicryl 13-031, PVA, Vilkyd 211, Vilkyd
resistance to the fungal attack. 270, Emulsion A, Emulsion B, Emulsion C, Emulsion D,
Sorlini et al. soaked Serena stone specimens in 26% Emulsion E, Emulsion F, and Emulsion G, following
methyl-phenyl silicone resin solution 11309 for one day.[29] the American military MIL-STD-810E method.[33] The
After the drying, some specimens were immersed in distill- resins were left to dry at room temperature three months
ed water where the resin is the only possible carbon source, before any fungi inoculation was started. The fungi used
and in malt broth with supplement organic compounds apart in the experiments were Aspergillus niger, Aspergillus
from the resin. Then these specemens underwent inocula- flavus, Aspergillus versicolor, Penicillum funicolosum, and
tion with eleven fungal species. After six months of incub- Chaetonium globosum. Optical and scanning electron
ation, visual and SEM observations, and stereomicroscopic microscope observations proved the fungal growth. In gene-
examinations proved that the only fungi isolated from ral, fungi seemed to grow very easily on alkyd, well on poly-
the stones were Aspergillus niger, Aspergillus flavus and (vinyl acetate) resins whereas acrylic resins seemed not to
Chaetomium globosum. These species were found only on be attacked at all. On all the samples, Fourier transform
treated and untreated samples immersed in malt broth sug- infrared spectroscopy analyses were carried out, but, com-
gesting that the resin did not sustain microbial growth. All pared to spectra of controls, no modifications in the spectra
treated samples underwent a minor loss of weight than con- were detected. Vibrational spectroscopy is an advantageous
trols, which meant that the resin was an efficient protective analytical tool for polymers and comprises two comple-
of stone. mentary techniques: infrared and Raman spectroscopy. A
recent investigation carried out by the same authors has indi-
cated that Raman spectroscopy is the more potential tech-
Paintings
nique for the study of products of degradation of synthetic
Synthetic polymers are mainly used for the lining and con- resins caused by biological agents.[34] In fact, because
solidation of paintings and are employed as binders and in the Raman signal arises from changes in polarisability and
varnishes.[30,31] the IR signal arises from changes in dipole moment, poly-
In order to evaluate the microbial degradability of some mer backbones generally have a strong Raman signal. In
synthetic polymers, commonly used in wall painting con- addition, Raman bands are narrower than IR bands so that
servation, as Klucel E, Mowilith DM 5, Mowilith 20, there is less overlapping of signals.
Mowiol 4-98, Paraloid B-72, and Primal AC 33, the
resins were incubated with microorganisms isolated from
Textiles
wall paintings.[32] The microbial agents were Aspergillus
versicolor, Aspergillus niger, Cladosporium herbarum, Synthetic polymers have been employed to make novel
Cladosporium sphaerospermum, Engyodontium album, fibres or as adhesives, consolidants and protectives of fragile
Penicillium aurantiogriseum, Penicillium chrysogenum, textiles.[35–38]
Trichoderma longibrachiatum, Debaryomyces hansenii, Unbleached Egyptian linen textiles were treated with the
Rhodotorula mucilaginosa, Bacillus subtilis, Bacillus following synthetic polymers already employed in the con-
licheniformis, and Rhodococcus fascians. The resins were servation of ancient textiles: Mowilith DM5, Tylose
dissolved either in 20% of aqua bidest. or in ethyl acetate MH300, Mowilith DMC2, Acryloid F-10, Paraloid B72,
and supported on glass slides. The resins were inoculated Lascaux 360 HV, Beva 371, Klucel G, Plexisol P-550,
with pure cultures and incubated for eight weeks at 28 8C. Plextol B-500, and Calaton CA.[39] The fungal strains
Primal AC 33 and Paraloid B-72 appeared visually almost inoculated, Alternaria tenuissima, Aspergillus nidulans,
not susceptible to microbial breakdown. A significant micro- Aspergillus terreus, Chaetomium globosum, Penicillium
bial growth was determined for Klucel E, Mowilith DM 5, asperum, Penicillium funiculosum, and Thichoderma viride,

Macromol. Biosci. 2004, 4, 399–406 www.mbs-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
404 F. Cappitelli, E. Zanardini, C. Sorlini

were previously isolated by Abdel-Kareem from ancient have been carried out to overcome the environmental prob-
Egyptian linen textiles and were allowed to grow for two lems associated with plastic waste. These investigations
weeks. The effects of the biodeterioration were measured lead to the isolation of synthetic polymer-degrading bacteria
by means of spectroscopic measurements (colour changes), and the discovery of genes encoding for enzymes involved
SEM observations, and changes in tensile strength and in the degradation of plastics.[41]
elongation. First of all, even if the majority of the polymers The majority of the investigations carried out on the
examined reduced the biodeterioration of the textiles, it was resins used in conservation are laboratory studies that
not completely prevented. The author demonstrated that attempt to predict field trials. Although it is not always
Beva 371 and Paraloid B72 were the synthetic resins most possible to reproduce real environmental conditions, the
resistant to fungal attack and Acryloid F-10 and Mowilith- main advantage of laboratory-scale research over field
types the most affected ones. trials is to note and record microscale changes.[28] The
Several types of plastic materials have become important evaluation of the biodeterioration effects was ascertained
as components of fabrics. Plastics made of polyethylene are by visual determinations, optical and electronic observa-
usually resistant to a microbial attack.[40] However, two tions, physico-chemical changes of the polymers, such as
types of plastic used extensively as coatings for textile loss of weight, and Fourier transform infrared spectro-
materials, plasticised polyvinyl chloride (PVC) and poly- scopy. Fourier transform infrared spectroscopy was gene-
urethanes, are susceptible to biodeterioration. In the case rally not able to show minor chemical alterations. The
of PVC, the polymer itself does not readily provide a technique probably requires additional refinements in
source of carbon for bacteria and fungi. The susceptibility order to detect this degree of chemical alteration. As pre-
of PVC formulations is usually related to other components viously mentioned, for this aim the use of Raman spectro-
rather than the resin, such as the plasticisers. Many of these scopy has been suggested.
additives are organic compounds of relatively low molec- Most of the researches carried out were devoted to the
ular weight. Microbial utilisation of the plasticisers may study of consolidants and protectives of stone materials.
cause the PVC coating to crack during use. On the other Although the use of synthetic resins as protectives could
hand, with polyurethanes the actual polymer is directly be enough to protect stone from pollutants and physical
capable of supporting microbial growth.[16] As a practical deterioration agents, they might be insufficient to prevent
measure, therefore, biocides should be added to both plasti- the growth of microbial species. The most studied synthetic
cised PVC and polyurethanes. product was Paraloid B72, an acrylic resin. It was generally
noted that acrylic resins were not affected by the attack of
biological agents, whereas other type of resins, such as
alkyd resins and poly(vinyl acetate) resin, under favourable
Discussion
conditions of temperature and relative humidity, are likely
If an artist may be aware of the durability of the materials to be susceptible.
used in his/her work, it should be a duty for a conservator An important parameter to consider when evaluating the
or a conservation scientist to know as much as he/she can biodegradation of a resin is whether the investigations were
about the long-lasting of the material used in the conserv- carried out when the resins were in solution/emulsion or
ation treatments as these have a significant effect on the when the resins were dried. This condition has to be check-
preservation of cultural heritage. It is thus important to have ed because the physical state of a molecule has an important
caution in using new materials and methods in contrast to effect on its biodegradability. The resin is less susceptible
old material and methods that have been used successfully to the attack when dried. Conservators are generally inter-
for centuries. If a material is stable and plays the role of a ested in the dried state because this is the state of the resin
protective from physical and chemical agents, this does not after the conservation treatment. Thus, the presence of the
necessarily mean that in the long term it will be the intelli- solvent, another source of carbon apart from the resin, may
gent choice from the biodeterioration point of view. In fact, lead to erroneous considerations. Another important factor
it has been assessed that microorganisms may exacerbate to take into account is the presence of other components
deterioration of materials. Potentially every material pro- in the formulation of the commercial product such as im-
vides a substratum upon which biological agents may grow. purities and additives. In this case the biological growth
In addition, the biodeterioration may act in synergy with on synthetic resin-based products may not be due to the
physical and chemical means of deterioration so that a assimilation of the resin but to other organic compounds.
damage can be dramatically increased. However, it is possible that the biomass, grown on the addi-
Biological attack of synthetic resins is a problem of major tives, produces unspecific enzymes that can attack the resins
economical importance throughout the world and has pro- (co-metabolic conditions). In any case, when additives and
vided a worthy challenge to microbiologists. On the other impurities are present, microbial growth can not be a certain
hand, there are more and more biodegradable plastics on indicator of the resin attack and other methods of investi-
the market. Widespread studies on biodegradable plastics gation should be applied.

Macromol. Biosci. 2004, 4, 399–406 www.mbs-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
The Biodeterioration of Synthetic Resins Used in Conservation 405

Different microbes play an important role in the attack [10] J. E. Potts, R. A. Clendinning, W. B. Ackart, W. D. Niegisch,
of synthetic resins. However, due to their adaptability to ‘‘The Biodegradability of Synthetic Polymers’’, in: Polymer
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