MATERIALS FORUM VOLUME 32 - 2008 Edited by J.M. Cairney, S.P. Ringer and R.

Wuhrer Institute of Materials Engineering Australasia Ltd

NANOPARTICLES AND THE CONSERVATION OF CULTURAL HERITAGE

A. Blee and J.G. Matisons* School of Chemistry Physics and Earth Sciences, Flinders University GPO Box 2100, Adelaide 5001, South Australia Email: janis.matisons@flinders.edu.au *Author to whom all correspondence should be addressed ABSTRACT This review examines some of the novel ways nanotechnology is being implemented today in the unexpected area dealing with the conservation of art and cultural objects. While such new technology is now being uniquely developed within this field, it is also true that historically centuries ago, nanoparticles have been cleverly used in art objects, and here todays science has been able to trace the elegant use of these precision-made nanoparticles from ancient times. The treatment of cultural objects is now changing with new treatments based around nanotechnology, incorporating not only the synthesis and use of functionalised nanoparticles, but also advanced sol-gel fabrication, and the use of polymers and gels. Synthesis of nanoparticles and gels useful in the cleaning and treatment of artworks are examined in detail, analysing not only their historical development but also their future potential. Finally a new concept in cleaning artwork is examined in greater detail. Here the pioneering work of Baglioni and Giorgi has laid the foundation for several innovative approaches, and these are examined in more detail in this review. the ancient Roman glass industry.5 Resembling the gemstone jade in direct light, and a ruby red colour when light is transmitted from within the cup, the unusual optical properties of the glass cup have received a great amount of interest.5 Although the quantities of gold and silver that give it its unique optical properties were acknowledged by B.S. Cooper in 1959, it wasnt until the late 1980s that Barber and Freestone revealed using transmission electron microscopy, that the Lycurgus Cup contained nanoparticles.5 X-ray analysis then further revealed that the nanoparticles were in fact a silver-gold alloy with a 7:3 ratio of silver:gold.5

1. INTRODUCTION The discovery and development of new substances can ultimately improve the quality of life. Indeed, this is the cornerstone of requests to the public by the scientific, medical and engineering communities for the financial support of long-range research. Materials science is one of the main connecting points between chemistry and engineering, and it is the principal area through which researchers in the chemical disciplines can influence technology. The key objective in making new and advanced materials is to find ways to generate new properties at three levels: the molecular level, the materials level, and the surface or interface level. Our objective here is to look at how nanoparticles and nanotechnology has impacted in preserving cultural objects, and more specifically the surfaces of such cultural objects. Nanoparticles have dimensions that are less than 100 nm.1 As a result of their very small size, they possess different properties to their corresponding bulk material.2 Their small dimensions are responsible for their large surface area, and this in turn results in a considerably increased surface to volume ratio, which then affects the nanoparticles physico-chemical properties.3 In particular they have distinctive optical, electronic, electrical, magnetic, chemical and mechanical properties.1,4 2. EARLY DAYS Nanoparticles are recognised to have been first used in the making of the Lycurgus Cup. The Lycurgus Cup is linked to 4th century A.D., where it was produced by 121

Figure 1. The Lycurgus Cup in 1958 with (a) direct light and (b) transmitted light from within the cup5 It was in 1962 that R.H. Brill working with the General Electric Company,5 suggested that the Lycurgus Cup was made by heat treating and applying the appropriate reducing reagents to glass containing minute amounts of gold and silver to cause the gold and silver components to form nanosized particles. However, this method would have been highly dependent on the

length of heating, the heating temperature, the atmosphere in which the heating took place and the proportions and oxidation states of certain elements involved in the process.5 As such, it represents a truly outstanding achievement by the Roman glass makers, as even today producing silver-gold alloyed nanoparticles with a 7:3 ratio, and applying such nanoparticles decoratively to a surface, has yet to be accomplished. 3. THE RESTORATION OF ARTWORKS USING NANOPARTICLES This review focuses on those nanoparticles now used in the conservation of cultural heritage, so the development of nanoparticles used in restoration of artworks needs to be considered. The most common nanomaterials used in conservation science are the water soluble inorganic nanomaterials, calcium hydroxide and magnesium hydroxide.3
Dispersions of commercial slaked lime (micron-sized Ca(OH)2 particles) in short-chain aliphatic alcohols show enhanced stability with respect to water, and so have been used to re-adhere lifted and detached paint layers in wall painting conservation. It is not unreasonable then to expect submicrometer particles of Ca(OH)2 to be more effective in wall painting restoration. Here, the smaller size of the particles should then ensure a greater stability of their dispersions, a higher penetration efficacy in the painted surface layers, and a very weak white glazing of the fresco surface after Ca(OH)2 application. In addition

nanoparticles.4 Then under nitrogen these nanoparticles are slowly heated to 265C, and vented to leave the MgO nanoparticles.4 Six years later,9 a similar method was used, to produce calcium hydroxide nanoparticles, also highly desired in conservation studies. The greater use of such a relatively simple sol gel technique, to generate water-soluble inorganic nanoparticles suitable for conservation, strangely still remains to be exploited. This may be due to the costly and hazardous metal-organic precursors10 used in the process, but more likely results from the lack of synthetic researchers working in this area. The sol-gel technique has also been deemed inconvenient10 and not economically acceptable for making these particular nanoparticles,10 but given the quantities needed in conservation this hardly seems justified. Rather, it seems to sadly reflect a lack of correspondence between experimentalists and conservationists. 3.2 Making Nanoparticles Through Heat Treatment in the Presence of Diols Salvadori and Dei8 have synthesised calcium hydroxide nanoparticles from both ethylene glycol and 1,2 propanediol. In this method, calcium chloride dihydrate is dissolved in either ethylene glycol or 1,2 propanediol and heated, while an aqueous sodium hydroxide solution is added dropwise. The rapidly stired resultant mixture is aged for 5-40 minutes (with 40 minutes giving the best results).8 The high boiling points of the diol solvents greatly assist in the process. The nanoparticles are then separated from the supernatant by hot filtration in vacuo, then washed with water, followed by isopropanol, before sonication and finally centrifugation (at 8000 rpm for ten minutes).8 This last step is usually repeated 5 times.8 Here removing the last traces of the initial diol solvents, and generating dry nanoparticles becomes the issue. Scaling such a process up would then exacerbate the problems associated with this final step. 3.3 Hydrothermal Treatment Another method commonly10,11 used to synthesise magnesium hydroxide nanoparticles is hydrothermal treatment. Magnesium hydroxide (brucite) is commonly used as the flame-retardant filler in composite materials, so this has been the preferred method for making such nanoparticles. This method employs a magnesium source, such as crystalline magnesium oxide,11 magnesium sulfate or magnesium nitrate,10 that would then either be mixed into a ethylenediamine-water solution10 or into water directly.11 Such a mixture is then placed in a Teflon lined autoclave, and heated to 160-180C for 2-24 hours.10,11 The magnesium hydroxide nanoparticles are then air cooled to room temperature, collected and washed with copious amounts of water.10,11 The final product is then air dried at 80C11 or in vacuo at 60C over 4 hours.10

to the conventional nanoparticles used in conservation, the pioneering work of Baglioni and Giorgi et al.6 recently synthesised novel magnetic nanoparticles in a chemical gel system, and this will be discussed in a later section of this review. While the synthesis of insoluble inorganic nanoparticles (sulfides, oxides and metallic colloids)3 has widely been published,7 water soluble inorganic nanoparticles are rarely reported.3,8 This results from the difficulty associated with achieving the high supersaturation degree that is required for nucleation of such nanoparticles,3 which is vital for their crystal growth.1 However, soluble inorganic nanoparticles have been synthesised using a number of methods that include the sol-gel technique, heat treatment of chelated diols, hydrothermal treatments, and the use of microemulsions and homogenous phase precipitation reactions. It is useful to consider each now in a little more detail. 3.1 Sol Gel Synthesis Water soluble inorganic nanomaterials, in particular magnesium hydroxide, were first systematically synthesised using the sol-gel technique in 1991.4 Here hydrolysis of a methanol solution of magnesium methoxide in toluene was slowly initiated with water overnight at room temperature.4 The resulting hydroxide gel is put into an Parr pressure minireactor vessel to produce the post-gel magnesium hydroxide 122

3.4 Formation of Nanoparticles Using Water in Oil Microemulsions Microemulsions were first used by Boutonnet et al. in 1982 to make metallic colloids having tightly controlled particle sizes.12 However, it is believed13 that the first water in oil microemulsion synthesis of a highly water-soluble material was reported 14 years later by Tracy et al. in 1996,14 although this work was based on the micron-scale rather than the nanoscale.13 The microemulsion approach seeks to exploit the ability to compartmentalize reactants at the nanometer level in discrete water domains, the structure of which is largely determined by the specific surfactant employed. There are many examples in the literature where the size and shape of the synthesized materials correlates to the size and shape of the organized assemblies from which they originated. However, since these early studies using microemulsions, water-soluble inorganic nanoparticles have been synthesised in water-in-oil microemulsions.7,13,15 Highly soluble inorganic and inert nanoparticles were made by using sulfate ions and calcium ions, contained within the pool of the water in an oil microemulsion.13 However, when synthesising metal hydroxide nanoparticles the conventional water-in-oil technique is inappropriate, as the high pH in the aqueous pool, resulting from the moderate water solubility of the hydroxide ions,7 causes the surfactants to become hydrolysed, and so results in a phase separation within the microemulsion.7 To overcome such problems, nonionic surfactants are employed, as they prevent counter-ion substitution at the microdroplet interface.7 As non-ionic surfactants are used, the systems containing the hydroxide ions need to be at less than 15C, to prevent phase separation.7 Here removing the last traces of surfactant, and so generating dry nanoparticles still remains an issue. 3.5 Homogeneous Phase Precipitation Reaction Several conservation researchers15-18 have used the homogeneous phase reaction to synthesize metal hydroxide nanoparticles. Such a procedure involves precipitating nanosized particles from a supersaturated organic solution (generally isopropanol) of the nanoparticle growth species.19 Here, a mixture of preheated counter-ion salt with reagent are rapidly stirred to promote the synthesis of nanoparticles.16 In order to isolate the nanoparticles, the precipitate is either cooled to room temperature under nitrogen and washed with water or lime water, or the precipitate is put into a moderate vacuum oven at 40C to remove the by-products.15-18 Both variations then disperse the metal hydroxide nanoparticles into isopropanol as a non aqueous solution is favoured in the deacidification processes used in art conservation.16 3.6 Overview of the Synthetic Methods Soluble inorganic nanoparticles were first synthesized in 1991. While there are several synthetic methods now 123

available for making such nanoparticles, the conservation field is preferentially uses homogenous phase precipitation, and to a lesser extent, the water-inoil microemulsion methods. It appears that the sol-gel technique has not been employed in the conservation field due to concerns with hazardous precursors that are costly and are not economically favourable.10 The sol-gel technique however does provide good control over the size and shape of the resultant nanoparticles. The hydrothermal technique is likewise acknowledged to give good control over the shape, structure and size of the synthesised nanoparticles.10 Furthermore, this latter technique produces high yields as surfactants are not required (such as in the water in oil microemulsion nanoparticle synthesis), and then need not be laboriously removed at the end of the synthesis.11 The hydrothermal technique is a simple10 way to produce nanoparticles in the 50-110nm11 range on an industrial scale. However, the temperatures needed here are much higher than those used in the homogenous phase precipitations, and the synthesis here generally takes at least 30 hours. Conservation scientists8 have considered using the water-soluble inorganic nanoparticles made from diols, but the high solubility of such particles in the diols causes difficulties. Often the diols remain adsorbed onto the nanoparticles after synthesis causing the particles to agglomerate.8 Although agglomaration can solved by peptization with propan-2-ol in an ultrasonic bath, removal of trace amounts of diol in the nanoparticle drying process is not trivial.8 Another disadvantage arises from the solubility of these nanoparticles in the diol solvents, which results in higher temperatures being needed during the filtration process to prevent the loss of any nanoparticles. However, compared to other methods, this method was the only one to report the selective formation of welldefined spherical and hexagonal nanoparticles compared to the usual hexagonal nanoparticles generated by the other synthetic methods. While the different shapes may not be a necessity in conservation of artworks, it may be useful in another field. Microemulsion synthesis of nanoparticles also results in good control of size and shape.20 However, separating the nanoparticles from the microemulsion remains difficult.20 Thus industrially, microemulsions are not economically beneficial as not all of the nanoparticles synthesised can be retained after removal.20 Lastly, the homogenous phase precipitation method provides a simple mechanism15 for producing watersoluble inorganic nanoparticles. Compared to the other techniques, it gives a broader range of size (making nanoparticles in the 50-200nm range, which are larger than other methods are capable of producing).16 This technique is easy to apply, as it provides a one step synthesis, compared to the multiple steps in current

conservation treatments and other nanoparticle syntheses.16 While the size range is on the high side of the nanoscale, the resultant nanoparticles still give successful results in the cleaning of artworks.15-18 However, decreasing the size of the nanoparticles by optimizing this technique may be useful as it will increase the chemical reactivity and penetration of the nanoparticles into the artwork, perhaps making treatment procedures quicker, which is a great step forwards due to the large amount of artworks that are degrading and are in need of treatment. Homogenous phase precipitation is the most commonly used nanoparticle synthesis pathway in generating the nanoparticles used for conservation science. It would then be expected that this method would possess some distinct advantages over other methods. Its simplicity, cheapness and the easily accessible temperature ranges give it the pronounced and distinct advantages over the other methods. 4. FACTORS INFUENCING NANOPARTICLE GROWTH The crystal growth of alkaline nanoparticles is dependent on the surface charge of particles, ionic adsorption onto surfaces and the chemical nature of ions used.16 With each of these variables affecting the crystal growth of alkaline nanoparticles, researchers have spent considerable amounts of time varying the parameters to optimise the growth of nanoparticles. Giorgio et al.16 looked into the use of different counter ions during homogenous phase precipitation. By varying the counter ion across magnesium persulfate, magnesium nitrate, magnesium chloride or magnesium sulfate, it was discovered that the counter ion plays a significant role in the mean size of the nanoparticle.16 Magnesium persulfate was found to yield the biggest particles (~200nm) with magnesium nitrate, magnesium chloride and magnesium sulfate (~50nm) decreasing the particle size respectively.16 This follows the Hofmeister series for anion trend (ClO4- > NO3- > Cl- > SO42-).16 These anions also act as surface modifiers that promote the nucleation and growth of crystal seeds in a continuous and systematic manner.16 The concentrations of the counter-ions has also been investigated.15,16 High concentrations of counter-ions promotes strong interactions between net surface charges of particles and the anions present in solution, which affects the nucleation and therefore the crystal growth as well.16 1M conentrations of salts compared to 0.2M conentrations yielded higher surface areas and smaller crystalline particles.16 It has also been found that the atmosphere that alkaline nanoparticles are dried in can affect their composition.17 For this reason, under the homogenous phase precipitation nanoparticles are now dried under nitrogen to prevent carbonation.17 It is also well known that temperatures play a crucial role in nanoparticle synthesis.15,16 Increasing the reaction temperature up to 124

~90C gives smaller particles, less agglomeration and higher symmetry of particles.15 During homogenous phase precipitation, both calcium hydroxide and magnesium hydroxide nanoparticles are usually dispersed into a non-aqueous solvent such as isopropanol.16-19 This enables the controlled release of hydroxide ions, which is vital in conservation treatments.17 Other treatments have shown the hydroxide release to be too quick.18 Nanoparticles, when dispersed in liquids, as compared to conventional powder treatments in conservation, are recognised in avoiding unsightly agglomeration. In wood and paper conservation treatments alkaline nanoparticles work by using the cellulosic capillary tubules, usually used for water transport in both paper and wood, to move the nanoparticles around the restored artefact without external help.17 The nanoparticles used are orders of magnitude smaller than the capillary tubes, and so are readily transported by capillary forces.17 It has also been shown that an excess of nanoparticles in isopropanol will not cause any resultant mechanical stress to the artwork.17 Within the artefact, the nanoparticles neutralise the sulphuric acid in the wood or paper (generating calcium sulfate), while the excess nanoparticles react with the carbon dioxide in air to produce carbonates, that are also neutralising agents.17 Often nanoparticles are not in excess, and so minimal carbonate residue is left behind.17 5. THE INTRODUCTION OF NANOPARTICLES TO ART CONSERVATION The use of nanotechnology in art conservation is a relatively new concept. It wasnt until 200115 that the first use of nanomaterials in this field was published. This initial report has gained significant praise for applying nanotechnology to a practical purpose (as distinct from a futuristic application) that showed immense improvement over pre-existing technologies. Since then nanotechnology has been applied to a variety of different cultural heritage conservation projects.6,21,16-18,22,23 It should be noted that each conservation treatment of an artefact needs to be individually assessed.22 The conservation treatment depends heavily on the materials used in the piece of art and the period it was from. Slaked lime was often used as a binder in wall paintings, frescoes and architectural materials.15,22,21,23 As conservation works on the theory of using compatible treatments, it is logical to use calcium hydroxide (slaked lime) in the conservation treatment of these artworks. Ordinary calcium hydroxide cannot be used as it leaves a white glaze over the artefact after application.22 Calcium hydroxide nanoparticles, on the other hand, do not leave visual residue on the artefact.22 Apart from neutralising the acidity that causes degradation in artefacts, the excess

nanoparticles that form calcium carbonate have been shown to further preserve paper artefacts that have been treated.17 This illustrates that nanoparticles not only deacidify valuable paper artefacts, but also control the long term effects of acid formation. It however needs to be considered as to whether any reactions or degradation could occur from the presence os such carbonates over time. If so then will another conservation treatment be needed to correct such degradation, as with the resins used in the past? Another water-soluble inorganic material, magnesium hydroxide, has also been used in conservation. These nanoparticles were used in the conservation of the Swedish Vasa Warship as well as various paper artefacts from the 14th, 17th, 18th, 19th and 20th centuries.16-18 Like calcium hydroxide nanoparticles, magnesium hydroxide nanoparticles also form carbonates as reaction product on exposure to the carbon dioxide in air.16 Magnesium carbonate reduces the rate of oxidative degradation of cellulose, caused by light irradiation, and so further enhances its usefulness in such applications.16 Here, it is important that the nanoparticles are dispersed in a non-aqueous solvent during paper deacidification. This is important because any ink of such documents or artefacts is generally insoluble in a non-aqueous solvent.18 Soluble inorganic nanoparticles are therefore usually dispersed into a non-aqueous solvent such as isopropanol.16,17,22 This solvent not only prevents agglomeration and gives minimal disruption to inks in paper treatments,18 but it also allows an easy way to apply the nanoparticles to artworks. The nanoparticles are applied by either brushing, spraying or immersing22 the artefact in the nanoparticle solution.16 Often such solutions then need to be removed, which can cause difficulties. However, as the reaction between carbon dioxide and any excess nanoparticles promotes a preventive treatment, in the form of carbonate formation, this is not really problematic.17 Furthermore, isopropanol has a lower boiling point than water, and will evaporate readily promoting the integration of the nanoparticles towards the restored artefact. Such a simple method of application also means that conventional and costly application techniques are no longer needed to perform conservation treatments.16 In paper deacidification, the Wei tO method has been commonly used.16 Nanoparticle synthesis using homogenous phase precipitation can be conducted in one step compared to two steps using the Wei tO method.16 The increased reactivity of the nanoparticle system, due to its nanosized components. increases the effectiveness of the deacidification process. Furthermore, current conservation treatments are only able to deacidify up to 0.5 cm below the surface (sometimes much less22). Nanoparticles, on the other hand, are small enough to penetrate right through artefacts via the capillary tubes present in wood, paper and some canvases.17 Using nanoparticles in conservation treatments, therefore, has the potential to 125

cleanse the whole artwork rather than leaving the core still degrading. Using nanoparticles has produced added benefits as they generate no colour change in contrast to other preventative treatments, such as using Paraloid 72, which leaves a yellow tinge over time.22 However, to reach its commercial potential the production of the nanoparticles needs to be scaled up and applied to whole projects. Once this has been achieved, conservators may be able consider using nanoparticles in much larger restoration treatments, which in turn could lead to the widespread usage of nanoparticles in place of gels in conservation. While there are a number of synthesis routes to make alkaline nanoparticles, researchers in the field appear to prefer using homogenous phase precipitation, due to its simplicity.15-18 Homogenous phase precipitation production of nanoparticles for conservation of artefacts, presents a cheap and environmentally friendly route to hydroxide nanoparticles, that can be easily applied in the field.16 Nanostructured materials therefore have the potential to make a great advances in the efficiency of cleaning artworks, due to their minute size and increased chemical activity and reactivity.24 Nanoparticle treatments used so far on cultural heritage materials have yielded successful results and confronted some of the problems with present day treatments.15-17 While there is still room for improvement in this area, it has opened up doors that show that there is indeed a connection between science and art. 6. CLEANING ARTWORKS The cleaning of artworks is a complex and challenging task due to the multiple materials used to construct an art piece.25 Furthermore, in the 1960s polymeric resins were coated onto paintings to endeavour to protect paintings, in the belief that these substances could be easily removed at any given time.26 However, these polymeric resins promoted a yellow tinge to artefacts and upon natural aging the resins lost their chemical and mechanical properties which in turn caused devastating damage to the artefacts.6,26 Such polymers were not easy to remove, and in some cases impossible to eliminate, from the surface to the artwork.26 In the past organic solvents,27 gel technology27 and laser28 techniques have all been used in the cleaning process to conserve our cultural heritage. The direct application of pure organic solvents to artworks through such techniques has resulted in the swelling of the original binding media and varnish layers.27 Organic solvents are also difficult to control in the cleaning process, resulting in the dispersion of solvent in unwanted areas, and possible solvent diffusion into the internal layers of the painting.6,27 For this reason, pure organic solvents are rarely used in conservation treatments today. Since 1980, gel technology has been used to successfully clean artworks, as it ensures a greater control over the liquid cleaning agents contact

with the surface.27 Furthermore, solvents in a gel system generally disallow the deep penetration that can occur using just pure solvents, which inevitably leave solvent behind in the core of treated paintings.6 Gel systems are also quite versatile, as various organic solvents and cleaning reagents can be gelled effectively, so giving the technique good selectivity.6 Unfortunately, gels do leave gelled residues on

surfaces because of their high viscosity, and these are difficult to remove.6 Gel cleaning techniques are also often inappropriate in the cleaning of porous artwork materials, such as the case with easel and wall paintings.6 Consequently, researchers have developed a novel magnetic nanoparticle gel system to be used in the field of art conservation.

Figure 2. Reaction Scheme for the Synthesis of the PEG-Based Polymer (MA-PEG) Used to Cross Link Particles6 7. AN EXCITING NEW DEVELOPMENT A novel magnetic nanoparticle gel system was made by crosslinking magnetic nanoparticles of CoFe2O4 into a copolymer based network of polyethylene glycol acrylamide.6 The magnetic particles for the cleaning gel system were derived from the Massart method developed in 1981.6,29 The synthesis of the nanomagnetic sponge was initiated by esterifying polyethylene glycol with anhydride (see Figure 2).6 The end groups of the product are carboxylic acids, The integration of the sponge into a cleaning device is particularly interesting. The magnetic nanoparticles are able to organise themselves into highly ordered superstructures, acting as building blocks. This actually explains the tightly bound structure within the sponge. As a result, the sponge can be easily moved with tweezers or cut with a knife,6 so that the size is always appropriate for the area that needs to be cleaned, which is a tremendous advantage. Bonini et al.6 used the nanomagnetic sponge together with a microemulsion. In order to load the sponge with the microemulsion, the sponge was immersed into a beaker of the microemulsion (see Figure 3).6 A variety of additives (different solvents, microemulsions etc.) can loaded into the sponge in this way, so fine tuning the sponge for a particular painting.6 Once the microemulsion has been taken up, it migrates to the surface of the gel, that which can then be directly reacted with magnetic nanoparticles.6 After the addition of a mixture of N,N`methylene bisacrylamide and acrylamide, polymerisation was initiated using ammonium persulfate, which resulted in the magnetic particles becoming embedded within a gelled network structure.6 Finally, the highly acidic magnetic sponge needs to be diluted with copious amounts of water to achieve a pH of 5.5, so that it can be applied to artwork. is in direct contact to the painted surface. The heterogeneity and pores of the polyacrylamide allow the microemulsion to move through the gelled network.6 At the surface, the microemulsion droplets solubilise the material to be removed, compartmentalize it and transfer it into the gelled structure.6 The gel is then removed using a permanent magnet. Since nanomagnetic particles have enhanced magnetic properties (compared to its bulk material, due to the differences in classical and quantum magnetism24), the magnetic nanoparticles within the sponge can be manipulated at a distance.24 This provides a distinct advantage in conservation, as it promotes a step in the treatment where the artefact does not need to be touched.

Figure 3: A Schematic Diagram showing how the microemulsion is loaded into the nanomagnetic sponge6 126

One particular application of nanomagnetic sponges was to clean a fresco painting that had been treated with Paraloid B72, 8 years ago.6 Paraloid B72 is one of the most widely used resins to protect paintings.6 It often however causes paintings to yellow, and this can be seen in the fresco painting studied (see Figure 5). It also can cause severe damage to artefacts. Scanning electron images and mapping through EDS of the fresco painting shows marked differences, after cleaning using the nanomagnetic sponge/6 FTIR confirmed the absence of polymer signals after cleaning.6 In Figure 4, (a) depicts a glossier smoother surface than that of (b); it almost seems to represent another completely different painting. The effect of the nanomagnetic gel application can also be clearly seen in Figures 4 (c)-(e). Over time, the gelled network slowly moves the Paraloid 72 residue

into the droplets, which are then transferred into the gel matrix. In the original report, we only see the application to a small piece of the painting. While the report considers the maximum amount of water that can be loaded into the gelled structure before it deteriorates, it fails to comment on the amount of residue that can be obtained using the magnetic nanoparticle gel. Clearly, the time that the painting is in contact with the nanomagnetic sponge will determine the degree of dirt/residue to be removed from the painting. However, it would be interesting to consider the capacity of dirt/residue that such a nanomagnetic sponge can contain. Does the sponge for instance, need to be continually removed, cleansed and then reapplied to areas?6

Figure 4: a) a SEM picture of the marbled surface treated with B72 before cleaning b) after cleaning c) mapping of calcium through EDS before cleaning d) 30 min after nanomagnetic gel application; and e) after the complete removal of the polymer6 The pioneering work of Baglioni and Giorgi6 has resulted in the formulation of a sophisticated cleaning process that aids the conservation of our cultural heritage. Current gel techniques have been exploited, by incorporating magnetic nanoparticles, that increase the potential of a gelled network to clean artworks. By incorporating iron magnetic nanoparticles, the cleaning process has been labelled gentle and simple. This new nanonetwork is at least as effective as previous gelling technology, but has the added advantage of being easier to remove, as the sticky properties of current gels make them very difficult to remove. The magnetic sponge can also be cut and shaped for easily application to sculptures giving much control and flexibility where the cleaning is taking place. The process has been reported to be used on churches and villas in northern Italy in early 2008,30 suggesting that other conservation structures will soon follow, as the Getty Conservation Institute, the Louvre Museum and the National Museum of Denmark have shown interest in using such innovative technology.26 One aspect that was not as yet been considered is the use of such technology in cleaning paintings that contain ochre pigments. Hematite and Goethite oshres are composed of Fe2O3 and FeOOH respectively. It would be worth investigating the effect that the magnetic nanoparticles and magnets have on such pigments, and whether they would be attracted to the magnetic nanosystem or the magnet used to remove the nanosystem. By changing the cross linking of the polyethylene glycol based polymer the adhesion of the gelled network to artefacts can be adjusted accordingly. It will be interesting to see the effects that the nanogels would then have on the residue on the painting and the painting itself.

Figure 5: (left) the white glaze shows the area treated with Paraloid with the circled area showing the area to be treated under grazing angle light (centre) gel treatment under normal light; and (right) area cleaned by removing paraloid B72 under grazing angle light6 127

Biographical Notes Alisa Blee is a final year student in Forensic and Analytical Science having recently completed her honours degree in conjuction with Flinders University and the South Australian Museum. Janis Matisons is the Chair of Nanotechnology at Flinders University, and the most recent recipient of the Royal Australian Chermical Insitutes highest award in applied chemistry, the Mark Wainwright Medal. Most of his career has been spent in industry, where he has brought some 76 products through to commercialisation. He became an academic at age 40, and continues in applied research incorporating nanotechnology, polymer and materials science with silicon chemistry. Acknowledgements The authors acknowledge the kind permission of the American Chemical Society in reprinting key figures from original articles. 13.

14.

15. 16.

17. 18. 19.

20.

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