e_conservation

the online magazine No. 7, October 2008

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the online magazine

One-Year Anniversary

In October 2008 e_conservation magazine celebrated its first year of existence, thus it is time for us to sum up our publishing experience. Looking back at the 6 issues we have published I can see that conservators do indeed have much to say. There are so many interesting things concerning our experience as professionals that are worth being made public and our task is to do just that. It has not been easy, but I can see an ongoing evolution in our approach, which is molded and shaped by experience. I believe that during this year our team, collaborators and committee members have done an excellent job. I want to thank them for having invested continuous efforts and for helping to maintain a high publication standard. On behalf of our team, I wish to thank all authors who submitted their papers during this last year to e_conservation magazine, and for sharing their knowledge and work with other professionals in the field. Often, their collaboration has continued and become a permanent and valuable support for the magazine. Obviously without you, our readers, and the website community members the magazine would not exist. I wish to thank you all for your numerous downloads and for the positive feedback, ideas and suggestions that we have received. The one-year anniversary is also the best moment to sort out our 2009 plans. On the practical level we are preparing to implement, next to the pdf format of the magazine, the html format that will allow the content of the magazine to be read online. On a more general level we are planning to give priority to the publication of research results, wishing to make new information available in a way which is easily accessible by everyone. We came to this conclusion after seeing that there is an acute need for a better synchronization between actual performed research, access to the outcome and current conservation practices. Plenty of institutions and researchers around the world perform high profile and relevant studies using some of the most advanced technology available, however, the transition between this research and the daily conservation treatments is still a difficult terrain. I believe that by continually publishing and giving free access to information we can help to fill in this gap. Conservators are aware that conservation is not a static field but a very dynamic one. Even though we apply our best knowledge to the conservation problems we face everyday, we also tend to implement the methodologies and treatments that we are most comfortable or familiar with. This reminds me a presentation I recently attended, where the Italian researcher Piero Baglioni shared his experience in helping conservators to establish the best approach to conservation practice. He pointed out a very important aspect: often the conservator may tend to damage the work of art by introducing harmful products or methodologies for lack of a better solution in cases where some sort intervention is unavoidable. This gap between the recent technological advances and our practice as professionals must be overcome and this is what drove us in the first place to publish the magazine. Controversies aside, I believe that free information distribution to professionals in an easy to access way such as the internet is what the future should hold for us. All we have to do is to want to share and learn. Rui Bordalo, Executive Editor
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editorial

www.prorestauro.com

INDEX

NEWS

CONFERENCE REVIEW Projects of T. K. McClintock Conservation of Fine Art and Historic Works on Paper 9 October 2008, Lisbon, Portugal
Reviewed by Rui Bordalo

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EITEC 2008 The 3rd International Meeting of Technologies Applied to Museology, Conservation and Restoration 23-24 October 2008, Porto, Portugal
Reviewed by Teodora Poiata

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ANNOUNCEMENTS UPCOMING EVENTS November - December 2008 CONSERVATION SCIENCE The Visible Image Is Not Always Correct The Differentiation of Layers by Optical Microscopy in Samples Cross Sections
By Carolina Barata, Antnio Joo Cruz and Marta Ferro

EVENTS ARTICLES

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TECHNOLOGICAL STUDIES The Church of Voronet Monastery Technical Considerations of the Mural Paintings
By Ioan Istudor

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MATERIAL STUDIES Forecast of Chemical Aging and Related Color Changes in Paintings
By Boris Zilbergleyt

CASE STUDY

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RED MAITREYA TEMPLE - LEH, LADAKH Mural Conservation Project (Part 2) - A Tibet Heritage Fund Project
By Anca Nicolaescu and Andr Alexander

BOOK REVIEW

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Conservation of Plastics Materials Science, Degradation and Preservation

Reviewed by Brenda Keneghan

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PROJECTS OF T. K. MCCLINTOCK
Reviewed by Rui Bordalo 9 October 2008 Lisbon, Portugal National Museum of Ethnology Organised by: rea de Papel do Departamento de Conservao, Instituto dos Museus e da Conservao (IMC) http://www.ipmuseus.pt/ On the occasion of the visit of the American conservator T. K. McClintock to Portugal, the Paper Area of the Conservation Department of the Instituto dos Museus e da Conservao (IMC) organised on 9th October 2008 a conference to present some of his projects. T. K. McClintock is the director and founder of Studio TKM, a private conservation enterprise located in Boston and specialised in the conservation of fine art and historic works on paper. The conference, divided in 4 individual lectures, turned out to be one of the most interesting I have attended so far: not only were the projects outstanding, but the author proved to be a very good speaker, retaining the audiences attention for more than 6 hours. The event was opened by Isabel Raposo de Magalhes, the vice-director of IMC, who welcomed T. K. McClintock and briefly presented to the audience his background and professional experience: he holds a masters degree in Conservation of Historic and Artistic Works from the Cooperstown Graduate Program, and graduated from Boston College with a bachelor's degree in Art. After he worked over a decade at the Northeast Document Conservation Center he established his private studio, specialised in the conservation of fine art and historic works on paper. Mr. McClintock started his speech with a brief presentation of his private studio, which has been in existence since 20 years and is specialised on the conservation of works on paper. An interesting aspect is that since the beginning the studio has been working with the same people, which is important for an effective team work based on "institutional memory", that is the accumulated
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Conference based on 4 lectures: . Observations on the Mutual Influence of Asian and Western Paper Conservation Practices; . Compensating for Losses in Historic Wallpapers; . Globe Conservation; . The Drawings of Frank Lloyd Wright: Observations on their Conservation.

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team experience. Several other aspects that are important to achieve a successful private conservation practice were underlined: the good communication among the conservators in the studio; the communication with colleagues in the same profession and with clients; the constant training by attending conferences and programs; and the research of collections and exhibitions in order to gain knowledge on practices and materials as well as familiarity with objects that are in good condition. 80 percent of Studio TKMs works come from public institutions and the rest from private collections. Their projects, half Asian and half western, are frequently very large, taking several hundreds of hours of work. An impressive number of case studies were presented during these 4 lectures. The first lecture - Observations on the Mutual Influence of Asian and Western Paper Conservation Practices - focused on how conservation methodologies greatly benefit from reciprocal share of experience. Mr. McClintock took a step into the past and reviewed some of the few available documentation resources as publications or training opportunities in the field of paper conservation thirty years ago, showing how the professional exchange has developed slowly but gradually with time. One important documentation resource for the author was the film The Art of the Hyogushi, produced by the Freer Gallery, which presented in detail the conservation treatments executed by Takashi Sugiura and his colleagues on several works on paper. Even if today the methods described in the movie are no longer in practice, for the 1970s they had an impressive impact on the western professionals. The fact that information about Chinese and Japanese studio practices started to spread was an important step in the development of paper conservation. Western professionals
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Photo by Aline Oliva

have learned from the experience of Asian paintings conservators on how objects respond to treatments, from their confidence in executing large scale projects as well as from the quality of materials, tools and procedures they are using. With time, the communication difficulty between these two cultures was overcome, western conservators going to Japan and Asian conservators coming to the west to mutually benefit from working and teaching experience. Today, Asian painting conservators benefit from research results and western developments such as the suction table for consolidation, synthetic resins consolidants, and cellulose ether adhesives among others. On their turn, westerners adopted Asian tools and supplies such as brushes, wheat starch paste and Japanese papers, and mounting, lining and reinforcement procedures. Above all, west conservators have improved their knowledge on the Asian objects, and have come to understand that there are many differences between Chinese and Japanese art objects, between their production technologies and implicitly, between their conservation methods and traditions. Mr. McClintock continued explaining the technologic differences between a scroll and a screen painting, showing that besides the inherent construction of the objects, their purpose and role greatly influences the exposure degree and thus their state of conservation. It was also emphasized that Asian works are seen as adaptable and their
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method of display can often be changed: handscroll sections, for example, can be remounted as hanging scrolls while hanging scrolls can be remounted as folding screens. Unlike for other works of art, these changes are seen as part of an already accomplished change of circumstances and not as a compromise to the integrity of the object. As a general conservation observation, the author has noticed that Asian paintings, even if not uniform in execution or condition, show a more regular pattern of problems than those encountered with western works. The rapport between the complexity of a treatment and the time spent by the conservator to perform the intervention was also discussed, as well as balanced solutions for conservation treatment. Among the interesting case studies presented, the intervention performed on a 17th century Ming copy on silk was described. The painting was mounted for display at Taliesin, the summer home and studio of Frank Lloyd Wright in Wisconsin. A particularity of this treatment was the partial removal of the linings but the maintenance of the so called "life layer" - the paper layer behind the silk. Also, the remounting was done using a honeycomb panel, which is resistant to contraction strength and allows only one side covered with layers of paper. This was done in order to fit back the painting into the original niche of the wall. In the end of his first lecture, Mr. McClintock paid tribute to Mr. Sugiura, who passed away in 2005 and with whom he had the honour to work in 1984. The second lecture - Compensating for Losses in Historic Wallpapers - dealt with the complex task that conservation of wallpapers is. In this case the conservation procedures for Asian and western works differ a great deal. There are several factors that make this type of conservation particular: the large size of the papers, the high level of exposure to degradation factors, the
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time consuming treatment process and the difficulty of treatment due to a limited access to the back of the wallpapers. A first arising issue concerning the conservation project is whether the treatment can take place in situ or the paper must be partially or fully dismantled and treated in the studio. Another very important factor that comes into discussion is moisture, where many of the conservation procedures rely on water and at the same time, water constitutes the base for forming the paper, for the colour binders and for the adhesives used for mounting paper on the wall. Mr. McClintock emphasised the risks arisen by moisture introduction, the importance of assessing objects tolerance to water prior to treatment and the ways in which it can be safely introduced. Several examples of treatment strategies were given, from in situ to studio treatments and from simple pattern papers to complex printed or refined papers with status of fine art. Again, balanced solutions for treatment options with respect to time consuming specific procedures such as inpainting were discussed. The conservators approach to inpainting is based on the use of transparent watercolours as these allow for a gradual effect in value, hue and intensity and because they are rather reversible when compared to acrylics. Concerning the reconstruction of loss areas, it is possible as long as another impression of the same paper is available. The available reproduction methods for historic wallpapers and their achieved level of authenticity and some of the factors that "legitimise" the use of inpainting in historic wallpapers were also discussed. The third lecture, and the most memorable one, was focused on Globe Conservation. These works on paper with three-dimensional format require a challenging and complex conservation treatment due to the fact that teche_conser vation

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nically they are made of different materials. Globes can be distinguished from other works of art by being objects with decorative purposes besides being cartographic records and historical references. For a public less familiar with this subject, Mr. McClintock made a short summary of their history, occasion on which he showed a beautiful collection of images of historic globes. Globes require a special conservation approach due to their construction technique which involves other materials in addition to paper. In their case, the paper covers the surface area of the three-dimensional object composed of several elements: core structure, plaster, paper, varnish, etc. The condition of a globe is mostly influenced by the state of the plaster sphere, which is normally affected by moisture, generating cracks and distortions, and in acute cases, compromising the state of the fragile layer of paper. Other often seen problems with globes are varnish and paper degradation due to abrasion against the horizon ring and as a reaction to the acidic nature of the wood, dirt deposits especially on the superior half of the sphere and varnish discoloration, among others. Concerning the treatment of the paper, similar procedures to those used for other works on paper are effective, but as the author noted "experience with a specific type of object teaches that there is a threshold of treatment, beyond which the paper should not be subject to additional procedures to achieve a theoretical, ideal appearance". The treatment is introduced gradually through the layers, generally starting with surface cleaning and sometimes partial or complete varnish removal and proceeding to the cleaning of the paper itself. This was described as a laborious process that can take over one hundred hours of work, generally under the microscope. Other complex treatments were also discussed, such as the removal and treatment of the gores, lining, filling, remounting and inpainting.
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Concerning this last complex operation, it is important to take into consideration the individual appearance of the object but also the overall appearance in relation to the other instances of the same edition. The rest of the globe elements are to be treated in rapport with the final appearance of the paper surface. When these elements are in need of complex procedures, the task is undertaken by other conservators with relevant experience. The last lecture was focused on The Drawings of Frank Lloyd Wright: Observations on their Conservation. The 20th century well-known architect produced an impressive number of works (437 constructed projects and around 1000 designs), major part of his drawings being in storage at the Frank Lloyd Wright Archives and at Taliesin West, the architects winter home. The collections gather some 20 000 drawings executed in "every available medium on a wide variety of paper and fabric supports with great purpose and originality". Commonly seen are drawings on tracing papers executed with graphite and coloured pencils, drawings in black ink or watercolour on thicker paper and illustration boards. In addition to this materials abundance, architects practices such as cutting and pasting sections of drawings onto other drawings and assembling several sheets with adhesive tape make this conservation process even more complex. The condition of the collection items greatly varies and a strategy to draw up a list of priorities in respect to the available resources had to be developed: drawings with adhesive tape, inadequately mounted or in very poor conservation state that require critical treatment constitute the highest priority; discoloured, distorted or very dirty drawings are the next priority and finally the drawings in stable condition, slightly distort or with torn edges that require a minor
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treatment. The drawings were treated in groups so that projects would maintain a homogeneous appearance. The treatment of tracing paper drawings may represent a challenge, as they are large in size and depending on how the paper was produced it can be easily affected by moisture and can greatly expand parallel to its grain direction. Methods of addressing problems like poor mounts, adhesive tape, stains, discoloration and losses and procedures like stain reduction, filling, lining, burnishing, flattening and inpainting were discussed in detail among others. Inpainting is done with transparent watercolour as the basic media, sometimes with the addition of pastels or metallic inks. Su-su, a material obtained from the brown distillation of boiled paper, is used by the conservator for inpainting. As mentioned earlier on, su-su is a very light stable product and relatively reversible when compared to watercolour. For the architectural drawings, this material was used to tone light areas that could occur after bleaching, and several other procedures for areas with losses or that required more extensive inpainting. In the end of the lecture, Mr. McClintock overviewed his 20 years long experience with this collection and the way treatment strategies have changed, acknowledging that the drawings of Frank Lloyd Wright have taught him "more about paper conservation than any other single body of work". After the lectures, Mr. McClintock answered a series of questions from a public that was still keen to learn more about his treatment strategies. To conclude, this exhaustive conference was a memorable experience for us all and we can only encourage the organiser to continue this sort of initiatives.
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EITEC 2008
the 3rd International Meeting of Technologies Applied to Museology, Conservation and Restoration
23-24 October 2008 Porto, Portugal Organised by: Sistemas do Futuro, Conservar-Inovar, ISQ and DCTP-FLUP http://www.sistemasfuturo.com/eitec/ Reviewed by Teodora Poiata

EITEC 2008, the 3rd International Meeting of Technologies Applied to Museology, Conservation and Restoration, took place on 23rd and 24th October 2008. This biannual conference has two main objectives which are to gather professionals in the 3 areas previously referred and to disseminate the latest scientific developments. So far the conference has been organised in three different cities of Portugal: Lisbon, Coimbra and now Porto.

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This 3rd edition of the conference was a joint organisation of four Portuguese partners: Sistemas do Futuro - Multimdia, Gesto e Arte, Lda.; Conservar-Inovar, Conservao e Restauro de Bens Patrimoniais, Lda.; Instituto de Soldadura e Qualidade (ISQ) and Curso de Especializao em Museologia do Departamento de Cincias e Tcnicas do Patrimnio da Faculdade de Letras (DCTP-FLUP, University of Porto). Due to the interest of the overall presentations and their rich diversity, it was considered more relevant to describe each presentation instead of making a critical review of the overall. The first speaker was Luis Bravo from the Regional Centre of Porto of the Portuguese Catholic University. In his presentation "Composed digital images in the study of works of art" he summarised four main techniques that use the juxtaposition of digital images to overcome known limitations of photography. The first technique is the use of high dynamic range (HDR) images applied to the digitalisation of wood sculpture x-rays in order to obtain better results in contrast and resolution. The second was the use of a strong flash light with specific filters and the merge of four photos to obtain a grazing light image in plain daylight. Next, he presented how by mosaic combination of several photos a super-resolution image can be obtained and some other ways to overcome the light difference among the several photos. Finally, he explained how the combination of photos at different depth of field, a technique called extended depth of field, is able to create close-up photos without depth of field distortion. These techniques are very interesting from the technical point of view, and may also be used for documentation purposes although how real these images are is still open to discussion. Researchers Alberto Proena and Joo Barbosa from the University of Minho gave a talk focused

Opening session, Armando Coelho Ferreira da Silva (FLUP), Maria de Ftima Marinho (FLUP), Gonalo Gonalves (CMP), Armando Dias and Fernando Cabral (Sistemas Futuro).

on objects digital representation techniques with PTM (polynomial texture maps): "Affordable Imaging technologies for Textured Representation of 3D artefacts". In the same way a grazing light photograph allows conservators to analyse a paintings surface, this technique combines in one single image light from several points of origin in order to obtain the best view and readability of a surface. The researchers referred that the project was developed within an international team and uses open software allowing an easy access to the technique. The presentation was truly educative as several examples were given, for example, its application proved to be successful in numismatics to identify some roman coins and
Luis Bravo, applying HDR in X-ray digitalisation.

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Alberto Proena and Joo Barbosa, revealing almost undetected stone engravings.

Pedro Manuel Ramos da Silva speaking about Media Art conservation.

to help to document the pre-historic stone engravings from Ca Valley (Portugal). As these images are obtained directly without artifices, this technique could be highly interesting for documentation purposes. Pedro Manuel Ramos da Silva, an art historian and researcher, introduced an often forgotten topic that is media art, with a presentation entitled "Media Art. Introduction to conservation and collection of electronic and digital art". The researcher started by making an historical overview of this type of art from the beginning of the 20th century to our days, including installations and video art and continued with a brief introduction to the problems that conservation of those media raise, namely the digitalisation and the archival of digital copies. The awareness of conservation of these new art forms must increase and this problematic should certainly be discussed more in depth. The presentation "Invisible technology and Museology excellence" was given by Isidro Moreno, a professor at the Faculty of Information Sciences of the Complutense University of Madrid. The researcher reflected on the use of technology in different museums, from Washington to Tokyo, and on the physical and conceptual barriers within museums.
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Javier Espadas Bardn is the responsible for the two websites of Fundacin Coleccin Thyssen Bornemisza. In the presentation "Museums Internet Visibility Research" he shared the history of the ThyssenBornemisza websites and performed an in-depth comparison between theirs and other websites of the most known museums worldwide. Independently of the collections importance and location, the foundation shows a growing interest to use the World Wide Web to disseminate its activities and to turn visitors and internauts aware of its presence. Continuing a session almost fully dedicated to museums and the internet, Pilar Gonzalo spoke about "Online Community-Building 2.0 for Museums: Challenges and Opportunities in a Global and Diverse World". She is a consultant specialised in digital services for culture and the Executive Director of the Lamusediffuse Project. The main question she raised was "Do Museums trust their users?". Although it is clear that museums dont, from "no flash" to "do not touch" signs, the underlining message of this presentation was the real need of museums to work with the community. She also presented a case where only a little effort and access to the internet were needed to surpass institutional work. In particular she noticed that museums in Libya, which is still under dictatorship,
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Pilar Gonzalo, "Do museums trust their users?"

were not listed in AFRICOM nor easily found on the internet. Through several contacts and emails she was finally able to list several interesting museums that otherwise no one would even know about except if they would really visit those places. David Policarpo, representing the private company Digitrace Portugal, presented a talk focused on the use of radio-frequency identification (RFID) to mark and to trace stolen works of art. During his presentation he overviewed other marking methods as well and noted that the digitrace system was first applied by Vincent Peyronnet to works of art. The fact that many stolen works of art are retrieved by authorities but their provenance remains unknown or their owners do not provide sufficient ownership proofs was also noted. Jos Manuel Gaspar Nero, from Instituto Superior Tcnico, approached the rehabilitation of urban built heritage. His presentation summarized his personal reflection on the actual problematic of urban rehabilitation in Portugal. He mentioned not only the recent rehabilitation of historic buildings, such as Lisbons Castle among other monuments, but also the present and future rehabilitation of todays constructions. Indeed, the change of paradigms and the actual trends lead to a lack of sustainability. This is a required discussion in todays chaotic city.
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Joo Carlos Santos, architect at IGESPAR, the Portuguese public institute responsible for architectonic heritage, summarized the 20 years rehabilitation process of the 11th century monastery of So Martinho de Tibes, in northern Portugal. Sold to the private sector after the nationalisation of the Church property in the late 19th century, the monastery was bought by the Portuguese State in 1986. After a century of low maintenance and even a fire incident, the monastery is being requalified at the moment so it can be occupied again by a monastic order who will provide services to the community to help its maintenance. Closing the last session of the first day, Jose Antonio Teran Bonilla, architect from the Faculty of Architecture of the National Autonomous University of Mexico, spoke about a local rehabilitation project of the 17th and 18th century neighbourhood of San Jos, the historical centre of Ciudad de Puebla. The first speaker of the second day was Antnio Portugal from the Faculty of Sciences and Technology, University of Coimbra. His presentation was dedicated to the study of fungi on historical documents from the archive of University of Coimbra. The project focused on the identification of fungi through DNA study and the implementation of treatment methods based on gamma radiation.
Joo Carlos Santos, presenting the rehabilitation of the monastery of So Martinho de Tibes.

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Lusa Botelho, from the Technological and Nuclear Institute (ITN) and ITNs spin-off CHIP, presented hygienisation procedures by the use of gamma rays in ITNs facilities. Gamma radiation interferes with the genetic material of cells and it is being used to kill insects and microorganisms in several applications. Some examples were given concerning the use of this method in conservation for wood sculptures hygienisation. The subject of long term effects was raised but further research is still required. One of the most interesting presentations was given by Hans-Christoph von Imhoff, a paintings conservator-restorer and coordinator at ICOM-CC, who presented "Conservator-restorers of material cultural heritage - Aspects and development of their profession since WW II". Mr. von Imhoff summarised the history of the conservator profession, with a special focus in the creation of major European institutions and the international ethics charts. Speaking about education in our profession, he mentioned that while some European country's universities tend to merge successfully the theoretical with practical knowledge, others still tend to overestimate the value of the theory. He observed a lack of balance between "brain and hands" in plenty of universities that offer conservation degrees. Thus, there are many conservation graduates that know how to prepare "very good thesis" but in fact they have lack of experience and limited manual skills. This serious problem requires universities concerted efforts in order to offer a solution without delay. A project involving the conservation treatments of historic lead seals appended to parchments from the Archive of the University of Coimbra was presented by Catarina Isabel Santos, a chemist from the Department of Chemistry from the University of Coimbra. Their collection includes several seals from diverse centuries presenting different
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Paula Menino Homem, Maria Lusa Botelho, Hans-Christoph von Imhoff, Antnio Portugal and Catarina Isabel Santos. Discussion panel after the morning session of the second day.

alteration states that are not directly related to their natural ageing. As the main problem of the seals is related to the transformation of lead into lead salts, the project aims to characterise the source material through non-destructive analysis by XRF. The project included the reconversion of the lead salts into lead through local electrolytic reduction while the natural fibbers were protected with cyclododecane. The archival conditions were also changed in order to better preserve the lead seals. Although this project uses already established techniques, it is a new treatment in Portugal. The next intervention was performed by Rui Bordalo from Instituto de Soldadura e Qualidade (Portugal) who introduced to the public the effects that ultraviolet laser radiation induces in pigments, with a focus on the analytical characterisation of the alterations. Irradiated and non-irradiated pigment samples were analysed by several techniques, among which infrared and Raman spectroscopy, SEM-EDX and colorimetry. Although the effect of laser radiation in pigments is a broad area and several studies have already approached this subject, this study is far more comprehensive than others. The samples were produced in order
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to reflect those of a real painting, including pigments mixtures and artificial aging equivalent to several decades of exposure in museums conditions. The chemical and physical changes induced by the 248 nm laser to pigments and linseed oil were discussed. Carlos Surez from the private company ECOMOR presented the advantages that cryogenic cleaning has on stone and metals. The cryogenic cleaning is based on the ejection of solid CO2 with compressed air. It was a rather interesting presentation as it included several video demonstrations of its cleaning power and other advantages were discussed. However, data of possible disadvantages in the removal of selected layers in cultural heritage artefacts and its impact on long term was not available. Piero Baglioni, from the Department of Chemistry and CSGI of the University of Florence is a key player in the conservation field. His outstanding presentation was entitled "From micelles to microemulsions, gels and responsive nanomagnetic gels: when hard and soft matter merge together". Dr. Baglionis procedure of cleaning works of art using nanomagnetic sponges was last years news after its testing in the laboratory proved successful.
Piero Baglioni, speaking about the use of nanomaterials in conservation of works of art.

The technique was described as being based on nanoparticles made of cobalt and iron oxide which are mixed into a polymer gel, creating a magnetic sponge. Its application was demonstrated by a fascinating video showing a very simple process of coating a surface with a few drops of gel and its further removal by a magnet, after it had dissolved the dirt from the surface. The author also presented a summary of his 2 decades experience and research dealing with nanomaterials and their application to cultural heritage. Images from the conservation treatments applied by him and his team on mural paintings ensembles in Italy and Mexico have showed that this technology is indeed a real advance in the field of conservation, due to the outstanding recovery of the paintings from their advance state of decay. The conference's last speaker was Cristina Nabais from the Centre for Functional Ecology from the University of Coimbra. This biologist presented some results from a project that aimed to study the wood species from sculptures belonging to the collections of the National Museum of Ancient Art (Lisbon) and from the Gro Vasco Museum (Viseu). The project aimed to identify and later to correlate wood species according to their provenance and attribution with the history of the forest and the historic wood commerce. In spite of the obvious relevance of this study for the two reference collections that it was performed for, I believe such a project should be continued and extended to include more elements in order to widen its representativity. The event was well planned, the EITEC organisers giving attention to each detail and taking advantage of the historic city of Porto that is worth to be visited. The warm atmosphere and the comfortable scientific and social environment made this conference a very pleasent experience. We look forward to attending the next EITEC edition.

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NEWS

GCI BULLETIN
The Getty Conservation Institute (GCI) is a wellknown institution devoted to the development of visual arts conservation. Recently, the institute launched the GCI Bulletin, a free bimonthly ebulletin. As announced, "It will complement the GCI's print newsletter, Conservation. Published six times a year, the GCI Bulletin offers updates on our events, science and field projects, educational initiatives, and publications and videos". The first and current issue can be consulted at http://www.getty.edu/conservation/publications/ bulletin/current.html. The bulletin is divided into two main areas. The "projects and activities" section contains information concerning GCI related events. Among other events, this first issue highlights a forthcoming roundtable forum on Managing Urbanization and Conservation in Cambodia and a symposium on Panel Paintings to take place in 2009 at the Getty Center. The "publications, videos, and audio" section presents information related to media news. The first issue contains announcements such as the publication of the book The Craftsman Revealed: Adrien de Vries, Sculptor in Bronze which is the technical study of twenty-five bronze sculptures, the latest issue of Conservation and the GCI newsletter. You can also read about the most recent acquisition of GCIs Research Library and watch a seven-minute video on Asian organic colorants. If you wish to subscribe the GCI Bulletin please visit http://www.getty.edu/subscribe/ gci_bulletin/index.html.

The News section is publishing the most diverse information on cultural heritage topics, such as on-site conservation projects reports, conferences, lectures, talks or workshops reviews, but also course reviews and any other kind of appropriate announcements. If you are involved in interesting projects and you want to share your experience with everybody else, please send us your news or announcements. For more details, such as deadlines and publication guidelines, please visit www.e-conservationline.com

The Getty Conservation Institute

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The events in this section are linked to the original homepage of the organisers. In case the event does not have an individual page, the calendar of events will open at www.conservationevents.com. Click on "Read more..." to find out more details about each event.

Sharing Conservation Decisions. 2008 November 2008

International Course
Date: 3-28 November Place: Rome, Italy The purpose of the course is to improve conservation decisions by involving the various professions and stakeholders, and ensuring transparency, clarity, and the effectiveness of the process. It is designed for any professional actively involved in heritage conservation. Read more...

Permanence in Contemporary Art: Checking Reality November 2008

Date: 3-4 November Place: Copenhagen, Denmark The seminar, which will encourage interdisciplinary exchange between museum professionals including conservators, art historians, artists and others, will take place in conjunction with Reality Check, an exhibition at Statens Museum for Kunst, opening fall 2008. Reality Check will act as a thematic springboard for the seminar, addressing issues related to content, material, time, exhibition and context exemplified by works in the exhibition. Read more...

Lessons in Anatomy Made Easy

Anatomical models in scientific and cultural context
Date: 6-7 November Place: Leiden, The Netherlands Museum Boerhaave organises on 6-7 November 2008 an international conference on anatomical models in their scientific and cultural context. The occasion for this conference is the completion of the restoration of the papier-mache anatomical models of Dr. Louis Thomas Jerome Auzoux, one of the largest collections of this kind in the world. Read more...

Responsibilities and Opportunities in Architectural Conservation

Date: 3-6 November Place: Amman, Jordan Architecture and heritage are intertwined through conservation. Architecture is a container of heritage in the sense that anything related to history and culture had occurred in space and in a place, the raison dtre of architecture. A guiding hand in human endeavors, heritage is a record of cultural precedents in any society, and as such, it is a foundation for growth and advancement in any human discipline, profession, or industry. Read more...

Cultural Heritage Research Meets Practice

8th European Conference on Research for Protection, Conservation and Enhancement of Cultural Heritage
Date: 11-12 November Place: Ljubljana, Slovenia The main objective of the conference is to foster the exploitation and spin off of EU research results. New technologies, tools and devices will be presented through talks, posters, exhibitions and practical workshops. Read more...

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EVENTS

Museums and Disasters ICOM / ICMAH Annual Conference 2008 November 2008
Date: 12-16 November Place: New Orleans, USA This conference will explore the various ways in which museums document and interpret the direct and indirect effects on society of natural, economic, and military disasters. It will be held in a city that suffered a devastating flood in 2005 that killed 1,464 people and where recovery has been painfully slow. Special emphasis at the conference will be on recent history/contemporary events. Read more...

II International Congress of Experimental Archaeology

Date: 26-28 November Place: Ronda (Mlaga), Spain The second International Congress of Experimental Archeology is being held to meet two general aims: to set out the recent theoretical-methodological contributions in the field of experimental archaeology and, in the second place, to provide a place for archaeological researchers to meet and debate. Read more...

EAS - Eastern Analytical Symposium

Date: 17-20 November Place: New Jersey, USA The Eastern Analytical Symposium and Exposition is held each year to provide professional scientists and students continuing education in the analytical and allied sciences through the presentation of symposia of papers, workshops, and short courses. In addition, an exposition of apparatus and supplies allied to these sciences is held concurrent with the symposia. Read more...

Youths in the Conservation of Cultural Heritage - YOCOCU

First International Meeting
Date: 24-25 November Place: Rome, Italy Addressed mainly to young Architect, Conservation Scientist, Art Historians Conservator/Curators, Conservator/Restorer and others, consists of a two days conference: the first devoted to the policy and strategy to promote an active role of these actors in the conservation field, white the second, to give voice to young professionals to share experiences, studies and new researches. Read more...

17th International Meeting on Heritage Conservation

Date: 20-22 November Place: Castelln, Spain En esta decimosptima edicin las sesiones de trabajo de los 11 Grupos Cientficos siguen siendo inauguradas por profesionales de relevante prestigio internacional, mediante una conferencia que versa sobre los ltimos avances cientfico-tecnolgicos en el campo de la conservacin y restauracin de Patrimonio. La conferencia contar con la presencia de Ren Larsen, de ENCoRe, y Jan Wouters del IRPA entre otros. Read more...

VAST2008 - International Symposium on

Virtual Reality, Archaeology and Cultural Heritage
Date: 2-6 December Place: Braga, Portugal VAST2008 continues the tradition of excellence in the VAST symposia for technologies in service of cultural heritage. This year's symposium emphasizes the ephemeral nature of the subject of our disciplines, namely the tangible/ intangible cultural heritage artifacts - archaeological remains, buildings, manuscripts, etc. - and the new virtual heritage artifacts we are producing in order to document, analyze, visualize and share our pasts through digital means. Read more...

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December 2008

November 2008

EVENTS

Measuring the Value of material Cultural Heritage December 2008

Second HERITY International Conference
Date: 3-5 December Place: Rome, Italy Read more...

Pest Management in Practice

Date: 10 December Place: Glasgow, Scotland, UK The event comes in continuation of the previous Read more...

The Conference is aimed to make possible to exchange ideas and experiences at an international level on the aims, possibility to measure, and the ways to describe the concept of Value related to material Cultural Heritage open to the public (Monuments, Museums, Archaeological sites, Libraries and Archives) from different points of view;

pioneering conference "2001 - A pest odyssey" held at the British Library. In this new meeting, in Glasgow in 2008, we hope to build on the success of the first workshop and introduce new IPM topics from the northern part of the UK. One of the most important tasks of this workshop will be to enable people to share and discuss their problems and successes and then to formulate a set of guidelines and priorities for future work and research to make IPM even more effective.

Se coordonner en cas de sinistre : mtiers, tutelles, rseaux

Comit franais du Bouclier Bleu - Journes d'tudes
Date: 4-5 December Place: Paris, France Le Comit franais du Bouclier Bleu sest donn pour mission linformation, la rflexion, lchange des connaissances et des mthodologies auprs de lensemble des personnes pouvant tre concernes, au titre de leur responsabilit professionnelle ou citoyenne, par une action face aux risques majeurs encourus par les biens patrimoniaux. Read more...

Material Worlds Date: 15-17 December Place: Leicester, UK A conference in honour of Professor Susan Pearce University of Leicester Professor Susan Pearce is an internationally renowned professor of museum studies and historical archaeologist, who has had a long and important association with material culture studies both within and beyond the museum. The conference is focused on Professor Pearce's contribution to the field with a significant material culture studies conference and the subsequent publication of a volume of essays based on the conference papers. Both the conference and the volume will explore agenda in theoretically-oriented material culture studies. We are now inviting the submission of abstracts. Presentations will address or inform approaches to theorising relationships between people and the material world. The range of potential themes is broad, and might include embodied experience and sensory engagements, the agency of and distinctions between objects and persons, the construction of value, etc. Read more...

The Sixth International Conference on Science and Technology in Archaeology and Conservation
Date: 8-14 December Place: Rome, Italy The main theme of the 2008 conference will be Documentation and Risk Management of the Cultural Heritage (CH). While documentation has long been recognised as an important tool for Cultural Resource Management and the Conservation and Preservation of CH sites and artefacts, it is gaining more and more importance in Risk Management. Read more...

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December 2008

article

AREAS OF PUBLISHING Conservation Treatment

Mural Painting Painting Stone Sculpture Textiles Paper / Documents Photography Metals Tile / Ceramic / Glass Furniture Music instruments Ethnographic assets Archeological objects

Conservation Science
Scientific research Material studies and characterisation Analytical techniques Technology development Biodeterioration State-of-the-art Reviews Art History, Iconography, Iconology, Chemistry, Physics, Biology, Photography, Cultural Management, Museology, Computer Science, Legislation and Juridical Processes, Conservation Policies and any other field applied to Conservation and Restoration of works of art.

Preventive Conservation
Theoretic principles Case studies

Documentation in Conservation
Standardisation Documentation methods Data management

Conservation Theory
Ethics Conservation History

Find out more:

www.e-conservationline.com
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THE VISIBLE IMAGE IS NOT ALWAYS CORRECT

The differentiation of layers by optical microscopy in samples cross sections

by Carolina Barata, Antnio Joo Cruz and Marta Ferro

The stratigraphic characterization of polychrome surfaces in works of art is frequently done through the observation of cross-section samples by optical microscopy (OM). Three examples that show some limits to this method are presented here. In samples where at first only one layer was visible, several strata were detected through electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). These and other examples ought to be taken into consideration by conservators, who should be aware of similar possibilities in other cases.

CAROLINA BARATA, ANTNIO JOO CRUZ & MARTA FERRO

At least since the middle of the 19th century, minute samples collected from works of art were mounted in resins, cut, polished and observed using optical microscopes [1]. However, only during the first half of the 20th century has this method been developed and employed more frequently [2,3]. Through the optical microscopy (OM) of cross sections from works such as paintings and polychrome sculptures, usually under a magnification of 100x to 300x, it is possible to determine the number and sequence of layers and to characterize each one of them with respect to matrix heterogeneity, particle size, color, shape and transparency, among other aspects. The information obtained is useful, for instance, for the characterization of artist techniques, the distinction between original materials and overpaintings, and the diagnosis of the conservation condition. As it is known by any conservator, many examples are found in countless publications concerning the materials of paintings and sculptures. Today, with the same goal in mind, the embedded cross sections are also analyzed through some advanced analytical methods, namely scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and mass spectrometry [3]. However, despite the extra information provided by these methods, particularly in what concerns the chemical composition, the examination of cross sections by conservators is usually limited to OM. The situation can be explained by a number of reasons such as the relative low cost of the equipment that is required, and to the fact that the information obtained in many cases is both easily interpreted and sufficient. In some situations, however, the images acquired by OM can lead to false conclusions. These situations are probably not that frequent, but it is important for conservators to be aware of this
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possibility, especially when false conclusions may have significant consequences. The observation of only one stratum by OM when several strata are in fact present, is probably the most common situation. In the context of a Masters dissertation that aimed to contribute to the characterization of the Portuguese polychrome wooden sculpture from the Baroque period [4], the observation of cross sections, both by OM and SEM with energy dispersive X-ray spectroscopy (SEM-EDS), led to the detection of some interesting cases. For OM, an Olympus binocular microscope, model BX41, equipped with an Olympus Digital C-4040 Zoom camera with infinity corrected optical system, was used. The analysis by SEM-EDS was done in Hitachi SU-70 UHR Schottky FE-SEM with samples coated with carbon. In some samples, according to OM, the ground layer was composed of one stratum. However, through SEM-EDS, particularly through the maps of elements obtained, it was determined that the ground was actually composed of several strata, as showed by the chemical differences or the limits that were detected between them. In that study, the conclusions about the real number of strata were important, since one of the aspects under research was the relation between the information found in art treatises and working contracts, according to which the ground should be composed of several strata, and the workshops practice. One example is the cross section taken from the blue vestment of a sculpture representing Saint Andrew, dating from the second half of the 18th century, and part of the collection of the museum of Santa Maria de Lamas (Figure 1). Although a certain heterogeneity in the ground layer was visible, it was not possible to subdivide it. However, as revealed by SEM-EDS it was composed of a first stratum, enriched in calcium and lead
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DIFFERENTIATION OF LAYERS IN CROSS SECTIONS

1 3 2 4

Figure 1. OM - cross section taken from the blue vestment of Saint Andrew (100x). At the top, layers identified by OM: 1 ground; 2 bole; 3 gold leaf; 4 paint layer. At the bottom, 1a, 1b and 1c correspond to three different strata with different composition identified by SEM-EDS in the ground layer.

Figure 2. SEM-EDS map of Ca of the cross section observed in figure 1. Figure 3. SEM-EDS map of Pb of the cross section observed in figure 1. Figure 4. SEM-EDS map of Al of the cross section observed in figure 1.

(Figures 2-3) (probably a mixture of gypsum and white lead), a second stratum, enriched in aluminum (Figure 4) and silicon (probably a mixture of clay minerals and other silicon compounds), and a third stratum, also enriched in aluminum and silicon but with a high content of lead (probably a mixture of the same compounds present in the second stratum with white lead). Another example is provided by the sample taken from the flesh area of a sculpture representing Saint Francis Xavier (Figure 5), which dates from the last quarter of the 17th century and belongs to the same collection. The brownish color on the
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top of the ground layer was first interpreted as being a result of the impregnation of that layer by glue. This interpretation was also supported by the fact that no significant differences in the particles size and shape were detected inside the ground. The maps of elements obtained by SEM-EDS, however, showed that this was not correct. Instead, they revealed that the ground is composed of a stratum enriched in calcium and lead (probably white lead mixed with a calcium filler) at the base (Figures 6-7), followed by a stratum mainly composed of clay minerals, revealed by its high contents of aluminum (Figure 8) and silicon.
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CAROLINA BARATA, ANTNIO JOO CRUZ & MARTA FERRO

1 3 2 4

Figure 5. OM - cross section taken from the flesh tone of Saint Francis Xavier (100x). At the top, layers identified by OM: 1 ground; 2 lead white; 3 paint layer; 4 - overpainting. At the bottom, two different strata identified by SEM-EDS in the ground layer: 1a mixture of calcium filler and white lead; 1b clay minerals, first interpreted as animal glue.

Figure 6. SEM-EDS map of Ca of the cross section observed in figure 5 (300x). Figure 7. SEM-EDS map of Pb of the cross section observed in figure 5 (300x). Figure 8. SEM-EDS map of Al of the cross section observed in figure 5 (300x).

The last example comes from a sculpture from the second half of the 18th century representing Saint Dominic, also belonging to the collection of the museum of Santa Maria de Lamas [5]. In the sample taken from the black vestment, a reddish layer of bole seems to be present between the layer of gold leaf and the ground, although the separation between the bole and the ground was not clear (Figure 9). The ground layer seems to be uniform, but the combined map of several elements, obtained by SEM-EDS, suggests that it may be composed of at least three strata, as some lines are observed that probably corresponds to theirs limits (Figure 10). Additionally, the extension of the bole layer in this map is clearly delimited.
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We must point out that, in principle, cases like these can also be detected by other methods. Ultraviolet microscopy, which involves the observation of a sample exposed to ultraviolet radiation through an optical microscope, is such an example [3, 6]. Its usefulness is particularly expected when a highly fluorescent material shows different concentrations in different layers. Stain tests directly applied on cross sections are also an accessible alternative to SEM-EDS [6]. In this case different materials should react in different ways to a specific reagent. As a conclusion, the main point that we would like to emphasize is that one should bear in mind that
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DIFFERENTIATION OF LAYERS IN CROSS SECTIONS

when only one layer is detected by OM, in some cases several other layers might be present and be detectable by other methods. Although several examples of this have already been published, we none the less think that it is important to draw attention to this fact in a clear and explicit way. References
1. J. Nadolny, "The first century of published scientific analyses of the materials of historical painting and polychromy, circa 1780-1880", Reviews in Conservation, 4 (2003) pp. 39-51. 2. J. Plesters, "Cross-sections and chemical analysis of paint samples", Studies in Conservation, 2 (3), (1956) pp. 110-157. 3. N. Khandekar, "Preparation of cross-sections from easel paintings", Reviews in Conservation, 4 (2003) pp. 52-64. 4. C. Barata, "Caracterizao de Materiais e de Tcnicas de Policromia da Escultura Portuguesa sobre Madeira de Produo Popular e de Produo Erudita da poca Barroca", MSc dissertation, Faculdade de Cincias da Universidade de Lisboa (2008). 5. C. Barata, A. J. Cruz, J. Carballo and M. E. Arajo, "Os materiais e as tcnicas usados numa escultura barroca, do Museu de Santa Maria de Lamas, representando So Domingos", Conservar Patrimnio, 6 (2007), pp.21-30. 6. M. Matteini and A. Moles, Ciencia y Restauracin. Mtodo de investigacin, Editorial Nerea - Junta de Andaluca, Guipzcoa - Sevilla (2001).
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Figure 9. OM - cross section taken from the black vestment of Saint Dominic (100x). At the top, layers identified by OM: 1 ground; 2 bole; 3 gold leaf; 4 paint layer. At the bottom, 1a, 1b and 1c correspond to the three different strata identified by SEM-EDS in the ground layer. Figure 10. SEM-EDS - map of elements of the cross section observed in figure 9.

CAROLINA BARATA
Contact: cbarata@porto.ucp.pt Carolina Barata, sculpture conservator, owns a bachelor's degree in Conservation and Restoration and a master's degree in Chemistry Applied to Cultural Heritage. Presently she is a lecturer at the School of Arts of the Portuguese Catholic University.

ANTNIO JOO CRUZ

Contact: ajcruz@netvisao.pt Antnio Joo Cruz, conservation scientist, received his Ph.D. in Analytical Chemistry from the Faculty of Sciences of the University of Lisbon. At the moment he teaches at the Polytechnic Institute of Tomar.

MARTA FERRO
Contact: marta.ferro@ua.pt Marta Ferro, specialist in electron microscopy, is currently working at the University of Aveiro and at the Centre for Research in Ceramics and Composite Materials (CICECO).
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THE CHURCH OF VORONET , MONASTERY

Technical considerations of the mural paintings
by Ioan Istudor

THE CHURCH OF VORONET MONASTERY

The church of Voronet Monastery is one of the many medieval monuments from Bukovina - a historical region located in northeast Romania that was built in 1488 by Prince Stephen the Great in only three months and three weeks, according to the commemorative inscription of the church. The church was built on a triconch plan with altar, naos and narthex and was painted in the same period. Later in 1547, the Metropolitan Bishop of Moldavia, Grigorie Rosca, added an exonarthex to the west end of the church and decorated it with mural paintings, together with all the facades. Although the number of churches from Bukovina with exterior mural paintings painted in the same period is large, many of them are only partially preserved. Among the most remarkable ones are the mural ensembles from Humor (1535), Moldovita (1537), Arbore (1541), Voronet (1547) and the most recent, Sucevita (1601).

The mural paintings from Bukovinean churches, particularly those with exterior mural paintings, have always produced a strong impression on those who have admired them. Their colours, brilliantly preserved after so many centuries, appear as a phenomenon and represent an exception due to their execution technique. Specialists were always impressed by the exceptional intensity of their colours, moreover since these monuments are located in a very harsh environment. To answer the many questions asked about the materials and techniques used in the execution of the exterior murals of churches from Bukovina, a series of technical research projects were started. The first studies started in 1963 at Voronet when samples from mortars, pigments and binders were analyzed by micro-chemical and chromatographic methods1 [1] and subsequently, in collaboration

1 Chromatographic analyses were performed according to

Margaret Hey [1]. Image 1. The church of Voronet Monastery.

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IOAN ISTUDOR

with other institutions2, through mineralogical analysis, spectroscopy and IR spectrometry. The first results on the controversial blue pigment and its alteration on the south facade - in the areas affected by moisture - were published in 1965 [2]. Until that date, there was no precise information supported by scientific research, but only speculations which have not been confirmed by subsequent studies3. The technological examination of the interior and exterior mural paintings from Voronet church focused on the technical and material elements that could explain the unusually good conservation state of the painting. The quality of materials used by the artists and the correct execution technique led to the completion of a painting that draws attention not only due to its artistic remarkable qualities but also due to its exceptional execution technique.

Research results The interior painting was executed according to the Byzantine technique, on a fresco plaster (intonaco) consisting of lime mortar with hemp tow, which was applied over another layer of plaster made of lime mortar with straw and chaff (arriccio), that had the purpose of making the wall surface even. The same traditional Byzantine technique can be seen at St. Sofia from Trebizonda (13th century) and Kariya amii (Chora) from Istanbul (1320). The same procedure was used at Voronet in the execution of the exterior painting made during Prince Stephen reign, such as the register with geometric motifs above the wall bench of the south facade (Images 2, 3). Traces of painting from the west facade of Prince Stephens church are still preserved in the porchs attic and on the eastern wall the inferior curtain decorated register. According to a fresco painting technique, the intonaco was applied in horizontal registers separated in pontate4 and giornate5 whose horizontal and vertical joint traces are visible in several places (Image 4) and constitute an undoubted proof of

2 Mineralogical and spectroscopic analyses were conducted

in 1963 by the university lecturer Dr. Dumitru Sandu and his collaborators from the Mineralogical Laboratory of the University of Bucharest and at National Research & Development Institute for Chemistry and Petrochemistry (ICECHIM) (analysis certificate No. 317 / 09.05.1966).
3 For subsequent research I benefited from the collaboration

of the architect and painter Ion Bals, whose knowledge in painting techniques was a real help in the interpretation of the chemical analyses results.
4 Pontata (Italian ponte = scaffold) is a term that defines an

area of wall painting executed in fresco, which usually corresponds to a scaffold floor, being delimited by horizontal plaster joints.
5 Giornata (Italian giornata = a day) is a term that defines a

Images 2 and 3. South facade. Decorative geometric motif located above the wall bench (painting from 1488).

wall painting area painted a fresco "in a day". The horizontal succession of giornate distinguished by vertical joints constitute a pontata.
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THE CHURCH OF VORONET MONASTERY

a fresco execution. The colours were applied after the intonaco layer was well compacted and the design was marked by incisions. Traces of these preliminary operations (trowel traces and incision) can be observed on the surface of the plaster in grazing light6 (Images 5-8). The durability of Byzantine frescoes is mainly due to the procedure of compacting the plaster previous to the colour application.
Image 4. Narthex, north wall. Decorative ornament painted on a 'pontata' joint. Images 5, 6. Narthex, north wall. Photos in direct light (left) and grazing light (right). Traces of compacted plaster and drawing incision.

6 In Byzantine technique, the compacting of plasters had the purpose of breaking the superficial crust of calcium carbonate that forms on intonaco, bringing to the surface the calcium hydroxide solution for a good pigment carbonatation. This provides the gloss and depth of tones but also a greater resistance of the fresco painting.

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IOAN ISTUDOR

Image 7. Narthex, south wall. Photo in grazing light showing the relief of the surface.

Image 8. Details regarding the execution technique.

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THE CHURCH OF VORONET MONASTERY

minium (red lead)

charcoal black

green earth

1 2 3 4 5 6

Altar Naos Narthex Exonarthex Exterior (1488) Exterior (1547)

+ + + + + +

+ + + + + +

+ + + +

+ + + +

+ + + +

+ + + +

+ + + + + +

gold + + + + +

No.

Location

Wall preparation (mortar composition for intonaco and arriccio plasters)

Arriccio: lime, straw, chaff; Intonaco: lime, tow, 3-6 mm arriccio lime, straw, chaff; Intonaco:lime, tow, 10-15 mm Arriccio: lime, straw, chaff; Intonaco: lime, tow Arriccio: lime, straw, chaff; Intonaco: lime, tow Arriccio: lime, straw, chaff; Intonaco: lime, tow Intonaco 3-13 mm, lime mortar, sand and brick dust, 32-62%

+ + + + +

Table 1. Pigments and plaster mortars.

Colours were obtained by mixing pigments with water, lime water or lime milk in order to obtain more transparent or matte layers. Pigments used are shown in Table 1. Except the black pigment obtained from charcoal, all the other pigments used are mineral substances, natural or synthetic: coloured earth with iron oxide hydrate (ochre), or anhydrous (red ochre), Fe, Al, Mg and K (green earth) hydrosilicate, red lead oxide (minium), copper minerals (azurite and malachite)7 [3], mercury sulphide (cinnabar), silicates (smalt)8 and calcium carbonate9 (white).

Cinnabar pigment was greatly used in the altar, naos and narthex, for both the garments and decorations curtains and red strips. In the painting of the exonarthex (added in 1547), predominant is the use of minium (red lead). Minium (Pb3O4) suffered here, as everywhere else where it was used in wall paintings (frescoes and temperas), a microbiological alteration transforming into lead dioxide (PbO2) of dark brown colour [4] (Image 9). Red ochre pigment was greatly used in all church compartments and is the only red pigment used in the exterior painting.

7 Azurite is a natural mineral substance, basic copper carbonate

[2CuCO3.Cu(OH)2] which is found in secondary deposits of copper minerals, associated with malachite, which is also a basic copper carbonate [CuCO3.Cu(OH)2] [3].
8 Smalt pigment is a synthetic silicate, a potassium glass

content. The smalt used at Voronet is slightly coloured and has a refractive index between 1.535 and 1.540. Smalt particles size range from 0,05 m to 0,19 m.
9 It has been determined by chemical analysis that the white

coloured with cobalt minerals that has been produced in various workshops according to local recipes, having in consequence different durability and various colours, more or less intense. Its colour varies according to its cobalt
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pigment is calcium carbonate. According to the handbooks, this could be obtained from rich lime dried in the sun, or from recovered old fresco plaster, in dust. Rich lime whitens the colours with which it is mixed thus its mixture with other pigments was avoided, being only used as pure white.

lime white + +

malachite

red ochre

cinnabar

azurite

smalt

ochre

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IOAN ISTUDOR

Regarding the blue surfaces (the famous 'Voronet blue'), they were executed with azurite pigment (basic copper-carbonate) on black background consisting of charcoal for two reasons: optical properties (to enhance the colour intensity) and isolation10 against the excessive lime alkalinity (Images 10 and 11). In the interior painting from Voronet, a mixture between azurite and smalt pigments was also used (Image 12 and 13). In the steeple, the quantity of smalt used varies, being predominant especially on the registers depicting cherubim, seraphs, prophets and liturgical angels. On the walls of all church compartments it can be observed that the amount of smalt mixed with azurite is very small. The presence of smalt in azurite does not appear to be accidental as a similar case was noted by the Italian researcher Paolo Benzi [5], quoting Dell Serra. Studying the work of Sodoma painter for the Monte Oliveto Magiore monastery (1505 - 1508), he considers that it does not correspond to the "canonical"
Image 10 (left). Stratigraphic section from "Tree of Jesse" scene. The azurite blue pigment applied over the black charcoal background can be seen. Image 11 (right). Azurite pigment, OM photography.

Image 9. Exonarthex vault. The alteration of minium (red lead) into dark brown lead dioxide.

10 The layer of black (charcoal) has a thickness between 30

and 60 m (measures performed in the non-degraded areas). Azurite particles size varies between 10 and 30 m. The actual thickness of the colour layer of the interior painting varies between 30 and 50m (and reaches over 100m in the exterior painting, in the superior registers which are more protected by eaves).

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THE CHURCH OF VORONET MONASTERY

Image 12. OM photography, smalt pigment structure.

a fresco technique and notes that "azurite, mixed with smalt was probably applied a fresco on an intonaco not completely dry (quasi completamente secco), perhaps with the addition of an organic binder" [5]. Traces of smalt in azurite are also present in the exterior painting from Voronet and Moldovita. It is possible that the initial amount of smalt has been higher, but its compatibility with the binder is smaller than that of azurite and thus it was mostly lost under climatic influences.
Image 13. Naos steeple (interior). Smalt pigment.

The green colour was obtained from malachite or green earth pigments. Malachite was used in the exterior and in the porch, while the earth green has been used very much in the interior as well as exterior painting. Again, its preponderant use for certain areas can be noticed: backgrounds, garments and floral decorative motifs, and its application was done mainly over a charcoal black background but also pure or mixed with charcoal black. The earth green used on the south facade 1488 exterior painting, register depicting geometric decorative motifs, shows a yellowishgreen11 [6] shade due to the influence of the capillarity humidity. This shade may belong to the original pigment colour or could have appeared as result of a partial alteration.

11 The pigment known as "earth green" contains glauconite

(green-yellow) and celadonite (green-blue) minerals. The colour of the pigment depends on its mineral content. At the same time the alteration of these minerals in goethite (yellow iron oxide, FeO(OH)) is possible [6].

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IOAN ISTUDOR

Exterior wall painting practiced since the end of the 15th century in Bukovina, as the former western facade from the time of Stephan the Great proves, reached its highest glory in the 16th century during the reign of Peter Rares. The exceptional paintings conservation state in the severe climate of Bukovina surprises even more as it is known that the blue pigment is the first one to fade away under the influence of climatic factors. The good conservation state of the azurite, malachite and relief decorative pearls on the garments should be primarily attributed to the use of binders and a special execution technique, different than that of traditional Byzantine fresco. The blue colour intensity shows on the one hand that the binder can not be lime (calcium carbonate) which turns white during the drying of the colours with which it is mixed. On the other hand, the glossy aspect and hardness of the mortars used for the pearls, in contrast to the plaster surfaces of the wall, also show evidence of use of other binder than pure lime. Most existing scientific studies as well as handbook descriptions refer to the interior painting technique. Known cases of outdoor murals, especially in Central Europe - with a milder climate than Bukovina, were executed with binders containing proteins (calcium caseinate) besides pure lime. This binders use is reported by Alexander Eibner (quoted by Mora and Philippot) [7, 8], especially in the 16th century, but their conservation state, particularly that of the blue pigment under the influence of climatic factors, is not yet known [8]. As previously mentioned the 1547 painting from Voronet was executed on a plaster based on lime, sand and brick dust12 that distinguishes itself by a special resistance to environmental conditions. The painting technique was certainly a mixed one: beginning with the application of a fresco backgrounds and continuing with the application of colours that contain organic, proteinaceous binders [9, 10], on a not completely dry plaster
34

(intonaco). Among the proteins used as binder, casein-lime combination is the one conferring a superior resistance. The mixture, called calcium caseinate, was made of fresh lime and cow cheese. To the superior resistance of the paintings have also contributed: - The special compatibility of the crystalline pigments (azurite, malachite, calcium carbonate) with the binder, compared with colloidal earth pigments (ochre, ochre red, green earth); - The fungicide effect of copper pigments (malachite and azurite) which prevent the development of micro-organisms that deteriorate the organic binders in wall paintings in favourable environments; - The superior mechanical resistance of calcium caseinate than the one of calcium carbonate. The use of a proteinaceous binder is proved by the formation of a specific reaction, known as biuret reaction, in which proteins in strong alkaline environment in the presence of copper ions show violet colour [11]. Copper ions can result from azurite or traces of other copper minerals that can be found sometimes with the pigment and that react chemically easier (Image 14). Regarding the application of azurite, it is possible that it was applied as described in Paolo Benzis article [5, 11]. Examining the stone inscription

12 The results of the chemical analyses performed in 1964 at

the Institute of Design and Research of Building Materials (IPCMC) on some samples of fresco plaster from the exterior painting of Voronet, sampled from the inferior register of the south and north facades are the following: 28.16 - 28.67% loss in calcination, 34.5 - 37.18% insoluble substances in HCl, 1.63 - 2.54% SiO2, 32.98 - 35.12% CaO, 0.06 - 0.24 % MgO, 1.11 - 1.67% R2O3. From the discussion had on that date with Prof. Dr. Al. Steopoe, it was concluded that due to the very small quantities of taken mortar samples (2-5 grams), the results have a local significance. Only average samples obtained from greater quantities of mortars can give results to characterize the properties of the plasters.
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THE CHURCH OF VORONET MONASTERY

Image 14. The north facade (to west), above the door. On the white stripe the violet colour can be observed (biuret reaction), which proves the presence of an organic binder.

Images 15 and 16. Exonarthex, east wall. Stone inscription, 1488 (left) and visible traces of azurite on the background of the letters (right).

above the entrance of the narthex (originally on the west facade of Stefans church), traces of blue colour can be seen on the background of the letters. The colour is azurite applied directly onto the stone, which was only possible by adding an organic binder in the colour (Images 15, 16). On the south facade (west to the entrance door) the presence of an organic binder in the colour layer is also demonstrated by the black colour of the Bishop Grigorie Roscas headcovering, which shows an intense and glossy aspect and is very resistance to exposure. This colour effect can not be obtained in fresco technique (Image 17, 18). Analysing the conservation state of the colour layers from the facades it can be observed that the deterioration prevails on the areas exposed to the wind - north and north-east. At Voronet, as well as in other churches with exterior painting from Bukovina, it can be seen that the
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Image 17. South facade, portrait of Bishop Grigorie Rosca. The headcovering of intense black tone can be noticed.

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IOAN ISTUDOR

Image 18. Detail of Bishop Grigorie Rosca portrait. The intense tone of headcovering can be noticed.

Image 19. East facade. Erosion of the colour layer executed with earth pigments in the background and garments area.

number of well preserved colours decreases gradually from east to north, azurite and malachite pigments being the best preserved ones, both in backgrounds and garments, while earth pigments (ochre, ochre red, green earth) have a smaller resistance (Image 19). The detachment of the colour layer, observed at all churches with exterior painting, occurs as a result of humidity migration from plasters, favouring soluble salts - especially calcium sulphate - to evaporate on the surface. Recrystallisation of calcium sulphate close to the surface in pores or microfissures, and the formation of dehydrated gypsum (CaSO4.2H2O), occurs with cca. 1.6 times increase in volume. This exerts pressure on the mortar particles, breaking their cohesion and the calcium carbonate crust from the surface, resulting in the detachment and exfoliation of the colour layer.
36

Also, the inferior registers are more deteriorated than the superior ones which have been protected by eaves. This phenomenon was the reason of eaves enlargement during the restoration works carried out in the 60s of the last century. The natural aging of materials can be seen at Voronet, as in other churches with exterior painting, by the particular exfoliation tendency of the layers containing organic binders. Examining the conservation state of the exterior painting it becomes obvious that the last three registers of the exonarthex added in 1547 (south and north facades) are better preserved than the areas painted in 1488 (Image 20). We believe the different behaviour of the paintings executed in 1547 is due to the colour layer formation conditions and not to the execution technique, otherwise impeccable. A possible explanation may be that the painting executed
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THE CHURCH OF VORONET MONASTERY

Image 20. North facade. The conservation state of the paintings from the exonarthex added in 1547 is superior to the areas built and painted in 1488.
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37

IOAN ISTUDOR

on the freshly built facades of the porch had benefited of a greater quantity of moisture and lime which allowed a slow pigment carbonatation, while the facades of the old walls had available only the environmental humidity and the intonaco lime (Image 20). Unfortunately the azurite, pigment with beautiful colour and great resistance in normal conditions, has been exposed to high humidity (by capillarity) and altered, transforming in malachite (green).

This phenomenon is the result of a change in the copper carbonate - copper hydroxide ratio from 2/1 (in azurite) to 1/1 (in malachite)13 [12]. A very important part from the inferior area of the scene "Tree of Jesse" on the south facade became green [2, 3] due to the long period of exposure to capillarity humidity (Images 21, 22). Another phenomenon of azurite alternation, this time due to the chlorine ions content in the intonaco (accidentally), can be observed as green

13 Under normal circumstances, azurite is stable if the

partial pressure of carbon dioxide in the air is greater than 2.4 mm Hg. Since the partial pressure of carbon dioxide in air is 0.24 mm Hg, azurite transforms in malachite in the presence of humidity [12].

Images 21 and 22. Cross-section of a sample from the area where azurite transformed in malachite (left) and south facade, azurite transformed in malachite in the inferior area of the scene "Tree of Jesse" due to capillarity moisture (down).

38

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THE CHURCH OF VORONET MONASTERY

Images 23, 24. Porch vault. Green spots of alteration (atacamite) are visible on the azurite sky background.

spots of atacamite14 ([CuCl2.3Cu(OH)2], basic copper chloride) [3] (or paratacamite) on azurite background, on a few scenes in the porchs vault (St. Apostle Filimon scene, Synaxarium day 22 November and others) (Images 23, 24). Conclusions The conservation works of the mural paintings from Voronet started in the last decades of the last century under the coordination of Prof. Dr. Oliviu Boldura and offered the opportunity of collaboration between researchers from various interdisciplinary fields (analytical chemistry, instrumental analysis, microbiology, art history) with conservators, for the application of scientific methods to conservation. The chemical analyses have determined the nature and composition of the materials used in the painting process (mortars, pigments, binders), have identified the causes of physical and chee_conser vation

mical altering processes of colour layers, have emphasized the process of azurite and minium alteration and provided knowledge on the execution technique. Based on the research results above and from literature, we can consider that the Moldavian painters, knowing the Byzantine technique and entering in contact with painters from Central Europe that used binders in lime colours, have combined the techniques of these two schools. The result of this mixed process provided the formation of a very effective protective layer of the surface and allowed a better conservation of paintings from Bukovina. We can also state that only due to the procedure employed by the Moldavian painters, the exterior decoration of Bukovinean churches is much more resistant to environmental factors when compared with Byzantine, Central Europe and all other exterior paintings, in general.
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IOAN ISTUDOR

Bibliography
1. Margaret Hey, "The Analysis of Paint Media by Paper Chromatography", Studies in Conservation, 3 (1958), pp. 183. 2. Ioan Istudor, "Un fenomen de alterare a culorilor in pictura murala de la Voronet", Revista Muzeelor, 2 (1), (1965), pp. 65 66. 3. Ioan Istudor, Notiuni de chimia picturii, Daim Publishing House, Bucharest (2007), pp. 92. 4. Julia P. Petrushkova and Natalie N. Lyalikova, "Microbiological degradation of lead - containing pigments", Studies in Conservation, 31 (1986), pp. 65-69. 5. Paolo Benzi, "La Pellicolo pittore nella pittura mural in Italia, materiali e tecnice esecutive dall Alto Medievo al XIX seccole", in Le Pitture murali (tecniche, problemi, conservatione). A cura di Cristina Danti, Mauro Matteini, Arcangelo Moles Centro Di, pp. 73 102. 6. Franois Delamare, Laurent Delamare, Bernard Guineau and Gilles-Serge Odin, "Couleur, nature et origine des pigments verts employs en peinture murale gallo-romaine", in Pigments et Colorants de lAntiquit et du Moyen ge, Colloque International du CNRS, Paris (1990), pp 103-116. 7. Paolo Mora, Laura Mora and Paul Philippot, Conservarea Picturilor Murale, Ed. Meridiane, Bucharest (1986), pp. 156. 8. Jean Rudel, Technique de la peinture, Paris (1957), pp. 16 and pp. 43. 9. Ioan Istudor and Ion Bals, "Contributii la cunoasterea materialelor folosite in pictura murala exterioara a bisericilor de secolul al XVI-lea din Bucovina si la unele probleme de tehnica", Revista Muzeelor, 5 (6), (1968), pp. 491-497. 10. C. Merticaru, I. Istudor, and Gh. Cimpeanu, "Investigation Concern the Outdoor Wall Painting on the 16th Century Monasteries from Bucovina, Romania", Art 05 8th International Conference on Nondestructive Investigations and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage, Lecce (Italy), May 1519 (2005), Book of Abstracts, pp. 184. 11. Ioan Istudor, "Alteration de la Couleur observees sur les peintures murales des eglises de Bucovine", in Colloque sur la conservation des peintures murales, Suceava, Romania, June (1977), pp. 21 25. 12. Gerhard Banik, "Green cooper pigments and their alteration in manuscripts or works of graphic art", in Pigments et Colorants de lAntiquit et du Moyen ge, Colloque International du CNRS, Paris (1990), pp. 99.

IOAN ISTUDOR
Conctact: bistudor@gmail.com

Born on November 14th 1928, Ioan Istudor graduated from the Faculty of Industrial Chemistry, the Polytechnic Institute in Bucharest in 1951 and since then, he has been continuously working as scientist in the conservation field. During almost half-century of continuous research, he performed analyses for more than 300 monuments and established the main research laboratories for conservation in Romania: in 1962 the first national conservation laboratory of the Historic Monuments Direction; in 1963 the laboratory of the National Art Museum of Romania and in 1983 the laboratory of the National Art University in Bucharest. He was certified as Expert by the Romanian Ministry of Culture in the research of several conservation domains, he was awarded several Excellency and Merit Diplomas for his entire professional activity and he was attributed the National Order, Knight Rank for his merits. From 1975 to 2002 he taught applied chemistry to Conservation-Restoration, Museology and Monumental Art departments of the National Art University in Bucharest. Since 1996 he is working as researcher for the conservation company Cerecs Art S.R.L. He has published a large number of articles and a book entitled Notions on the Chemistry of Paintings. He was granted for the patent of his discoveries: The procedure of obtaining a transparent calcium casein dispersion, Solutions for extracting and transferring mural paintings by strappo and The candle that does not produce smoke". *Part of the information in this article was presented at "Testimonies of living history" communication session, Voronet, 12-13 September 2008. Photos by Ioan Istudor, Anca Dina and Magdalena Drobota.
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40

FORECAST OF CHEMICAL AGING AND RELATED COLOR CHANGES IN PAINTINGS

by Boris Zilbergleyt

The article describes the potential application of thermodynamic simulation to the problems of chemical aging of painting. Qualitative and numerical results were obtained in a preliminary investigation by applying the method to various mixtures of pigments without and with atmospheric components. The results were compared to historic recommendations on incompatible pigment mixtures with about an 80% match regarding potential color changes in the aged mixtures of pigments. Results for the cadmium yellow-lead white and cadmium lemon-emerald green mixtures are illustrated by pictures, gradually showing color changes related to aging. The method of thermodynamic simulation can be a powerful tool to investigate old paintings, in developing new materials, in conservation and restoration, and to forecast some aspects of the aging of real paintings.

BORIS ZILBERGLEYT

Introduction Color is, obviously, the most important element in a painting but also the most sensitive to degradation factors. From fading to darkening, color changes of paint layers that occur with time can alter the entire appearance and perception of a painting. Painting collections in world museums abound with altered canvases due to internal and external deterioration factors and unfavorable conditions that occurred before they were placed in the controlled museum environment. Although external deterioration agents, such as environmental factors (temperature, humidity, ultraviolet radiation, etc.) and biologic attack are permanently putting works of art at risk, their impact can be controlled and limited in many cases. However, in the long term, the major reason for color change of a painting is the inevitable chemical aging of the paint layers [1]. These changes include alterations in the optical properties of binders, and in the chemical and structural composition of pigments due to chemical interactions between them, assisted by atmospheric species [2]. Chemical deterioration, resulting from these interactions appears to be immanent to the aging process. The aging patterns of paintings have been intensively studied, and seem to be quite clear on a qualitative level [3, 4]. Paintings are composed of a complex of grounds, pigments, organic binders, and varnish and in an ideal case the fresh paint layer contains well-encapsulated pigment particles. The particles are separated from the support (canvas, wood, etc.) by the preparation layer, from each other by the binder, and from the atmosphere by both the binder and varnish layer. As long as the ground, binder and varnish are intact, routine changes of paint layers are extremely slow. But even in the most favorable storage conditions, the upper layer often ages faster than the inner layers. Initially, aging leads
42

to a change in the optical characteristics of the varnish and to the formation of craquelure networks. Moisture and other atmospheric factors sharply accelerate chemical interactions between pigments and other components of the paint layer leading to intensive changes in its chemical and phase composition and to massive changes in the color, brightness and contrast of the painting. What can we do and to what extent can we prevent the chemical changes? Chemical aging of paintings has been extensively studied although a comprehensive understanding has not yet been achieved. We are aware of historic recommendations from old masters on the incompatibility of certain mixtures of inorganic pigments, such as lead white and ultramarine among others, based on the artists practical experience [5, 6]. The technical execution of a work of art is another important aspect to take into consideration, but in any case, we need to understand on a quantitative level the aging mechanisms of a painting. Thermodynamic Simulation Method The method of thermodynamic simulation consists of the computer simulation of possible chemical interactions within the paint layer to determine the ultimate chemical and phase equilibrium composition. It allows for numerical calculations of the most probable final composition of the paint layer, resulting from these interactions when all changes are over and the system rests at thermodynamic equilibrium. One can state that in old works of art most of the possible chemical processes, allowed by their pre-museum and museum storage conditions, are either completed or the relevant changes are already well pronounced. Knowledge of the chemical and phase changes in the layer may help to predict optical/color changes and structural damages such as detachment or flaking of the paint layer.
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FORECAST OF CHEMICAL AGING AND RELATED COLOR CHANGES IN PAINTINGS

The method can be implemented using most of the known simulation software; we used the simulation complex ASTRA-4 [7] and partly HSC Chemistry [8]. Atmospheric pressure (0.1 Pa) and a temperature of 293K (200C) were taken as simulation parameters. In case of pair mixtures of pigments, the mass ratio of main to admixed components varied from 10:1 to 1:1. Taking into account the relatively long lifetime of a painting, atmospheric air as a natural mixture of oxygen and nitrogen was present in the initial compositions up to 10%, with moisture up to 5% of the air mass and some typical pollutants like CO, CO2, sometimes SO2 and H2S up to typical concentrations for urban areas. In cases when not enough thermodynamic data was available to involve some complex pigments of interest into simulation, we used their essential and often the major color carrying fragments. For example, in case of lead white we used the data for lead carbonate only; in this case simulation was carried out with the fragment of the pigment with known data instead of the whole compound. The same situation occurred in case of ultramarine and several others. Though in most cases this was good enough to judge the possible color changes, the results of this work should be considered qualitative for manifesting the methods ability to predict and describe the chemical aging of paintings. Simulation Results For several chosen groups of pigments we tried chemical interactions within the group between the comprising pigments along with simultaneous interactions of these pigments with atmospheric components; lead white and zinc white with some pigments in presence of atmospheric components; oxide pigments in mixtures with sulfide pigments; special pairs of pigments to check the historic incompatible pigment couples, and some complex
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mixtures from Rubens palette. Among these mixtures, the incompatible pigments group is one of the most interesting in the light of this work. Corresponding results are shown in Table 1. In some cases, when both dark and white substances were formed together in the mixture, such as FeS, CaS, and Na2CO3 in ultramarine mixtures with ochres and umbers, it was difficult to evaluate if optical changes would happen. Also, gaseous reaction products are not shown in the table. Even with this restriction, in about 80% of the investigated mixtures the predicted possible optical changes have certainly matched the historic alterations. What is remarkable is that the method of thermodynamic simulation also explains possible reasons of the changes in terms of chemical and structure composition thus allowing for visual interpretation. Percentage of the matching Y/N compatibility results in Table 1 is high enough to prove the applicability of the method to the analysis of chemical aging of paint at least on the qualitative level. The quantitative results, even if more difficult to obtain, will definitely offer more information. Table 2 contains numeric simulation results of the incompatible mixture of lead white (represented by lead carbonate) with yellow cadmium (represented by cadmium and zinc sulfides). The abbreviations for colors are B for black, W for white or light colors, and Y for yellow. To account for reduced thermodynamic activity of the lead carbonate (PbCO3) due to its binding into lead white (2PbCO3.Pb(OH)2), its thermodynamic activity coefficient was reduced to 0.6 for simulation. One can see changes in the chemical composition of the mixture due to decay of input basic color carriers, certain structural changes due to the presence of new components, and drastic color changes in the presence of black lead sulfide. Figure 1 shows color visualization of the simulation results, RGB indices were calcu43

BORIS ZILBERGLEYT

lated using data for yellow cadmium from [9]. Mixtures color was calculated as weighted mean of their components [10]. Pigments Base Admixed Ultramarine Caput Mortuum English Red Lead white Cobalt Blue Dark Ochre Natural Umber Cinnabar Copper pigments Lead White Massicot Cadmium Yellow Lead Yellow Ultramarine Iron Oxides Umbers Terra di Verona Ultramarine Cobalt pigments Mn-Cd paint Cadmium Yellow Ochres Ultramarine Umber Copper pigments Umbers Darkening None Changing tone Not specified changes None Tone brightening Changing tone None Brightening Darkening None None

Table 1. Compatibility of various pigments in pair mixtures. N not compatible, Y compatible, Leg. - legendary, Sim. simulated. Black or just dark colored species resulting from the chemical interactions are typed in bold.

Known optical changes

Simulated New species able to change the colors Potential color changes

Compatibility Leg. N Sim. N N N Y N N Y Y N N N Y N N Y N N N N N N

Darkening

Na2CO3, PbS, PbO2 None Pb Pb, PbO none none Pb, CdSO3

Darkening

N N

None Darkening None None

N N N Y Y N

Blackening

Pb Pb, PbO, Cr2O3 none Fe, Fe3O4, CdSO3 Cd, MnS, CaS Cd, CdSO3, MgO Co, Na2SO4 Co Co FeS, CaS, Na2CO3 Cu2S, NaOH

Blackening

N N

None Darkening Probably none Darkening

N N N Y N N Y

Brightening Darkening

N N N

Cadmium orange/red
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MnO

Probably graying

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FORECAST OF CHEMICAL AGING AND RELATED COLOR CHANGES IN PAINTINGS

Table 2. Numerical simulation results for yellow cadmium lead white mixture chemical aging.

Species Initial amount, mol. Equilibrium amount, mol Color

PbCO3

CdS

ZnS

PbS

ZnCO3 CdCO3

R 256 159

G 185 139

B 137 113

1.000 0.500 0.500 0.538 0.378 0.160 0.462 0.339 0.122 W Y B W W

Figure 1. Color changes following chemical aging of 1:1 mixture of yellow cadmium with lead white, consequent stages at equal time intervals. The leftmost sample corresponds to a fresh mixture and the rightmost to the mixture, aged to the equilibrium limit.

Figure 2. Color changes following chemical aging of the lemon cadmium mixtures with emerald green, various initial mixture contents. The leftmost swatches show accepted colors of pure mixture components.

Figure 2 shows the aged samples of the cadmium lemon mixture with emerald green, compared to the initial colors (upper row); numbers on the swatches show initial moles ratio cadmium / emerald green in the mixture. Interestingly, that cadmium pigment almost totally disappears in all investigated mixtures after aging; its increase in the initial mixture leads to more and more pronounced grey color due to formation of dark, fine dispersed particles of Cu3As and Cu2O along with several white products. Chemical Aging of Some Rubens Pigment Mixtures Rubens was one of those rare artists who thoroughly wrote down the major components of the mixtures he used in various purposes, sometimes with a kind of functional names [11], that allows us to experiment with his palette. Qualitative results of the simulation of the mixtures aging in presence of normal air (with typical presence of moisture) are placed in Table 3.
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Conclusion This work presents the results of a computer simulation aging experiment in the field of paintings, where the information was collected from testimonies of old masters and from paintings, where precise initial composition may not be known. The data related to paintings aging and pigments compatibility is transmitted and may vary from one bibliographic source to another, sometimes without clear references. Certain information definitely can be achieved after centuries of natural aging or using accelerated methods, usually run at conditions different than the natural ones, such as elevated temperatures and moisture [1]. To the best of the authors knowledge, our approach was the first attempt to use an experimental computer simulation method to predict chemical aging. Discussing the results of this work, one should keep in mind that thermodynamic simulation brings about the ultimate results of aging potential chemical and structural changes providing that all possible interactions in the
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BORIS ZILBERGLEYT

Pigments Mixture color Neutral white base Lead white admixture

Initial mixture for simulation

Simulation results New species after aging Hg, PbO2, H2SO4 Hg, PbS, Cu2S, Na2SO4, Na2CO3 PbS, Hg, Cu2S, Na2SO4, Na2CO3, NaOH Fe, FeS, Pb, Cu, Na2CO3 CuO Possible changes Darkening

Flesh color

Lead white

Lead white, Cinnabar, ochre, cinnabar, ochre, organic black air Cinnabar, Lead white, krapplaquer, ochre, ochre, lapis ultramarine, lazuli, azurite, azurite, air organic black Azurite, Ultramarine, cinnabar, ochre, cinnabar, ochre, lead azurite, lead white, white, air organic black, smalt Lead white, organic black, Ochre, lead krapp-laquer, white, azurite, lapis lazuli, ultramarine, air smalt, azurit Lead white Azurite, white lead, air

Blue

Lapis lazuli, indigo

Yellow/ Brown

Ochre

Darkening

Green

Azurite, malachite

Darkening

Table 3. Predicted changes in various paint mixtures of Rubens palette.

ground-pigment-binder-varnish system are over, that is the whole system rests in thermodynamic equilibrium. Equilibrium compositions, in their turn, should be considered as the limit towards which the system moves, but not necessarily achieves it in reality. Chemical aging advances up to the latest stages of the painting lifetime but is just one of the possible contributors to the deterioration process. Although the scope of this investigation was restricted to inorganic pigments, the proposed method is applicable to analyze chemical interactions between any kind of substances including organic dyes, binders and grounds. The increasing abilities of computers essentially expand opportunities for simulation and output of the simulation results in such complex materials like paint mix46

tures. Besides that, the method can be used to investigate chemical behavior not only of a painting but also of any art materials that change by interacting with their environment. Although the method investigates only one important aspect of the aging of paintings, in certain cases its results can help conservators to achieve a better understanding of the aging behavior of compatible and incompatible pigment mixtures. Even though color alterations are generally accepted as part of the authenticity of a painting, this method may help to establish the appropriate conservation methodology. The application of the method of thermodynamic simulation in the field of aging is not easy because only rare pigments are chemically simple enough to have their thermodynamic properties ready in
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FORECAST OF CHEMICAL AGING AND RELATED COLOR CHANGES IN PAINTINGS

the regular thermodynamic data bases. Calculation or recollection of appropriate experimental information should be the first task prior to the method implementation. The author foresees many objections related to the results of this article. Among them, why most of the species, predicted in the run of that preliminary investigation, were never reported by previous investigators? Well, it could be that the works of art, investigated earlier on, didnt achieve the extreme stages that could be qualified as equilibrium in the context of this article. Or, what if they were just overlooked because nobody suspected them to be present? Who might be interested in using this method? We believe it can definitely help to investigate possible reasons for the changes that occurred, and how aging will develop. It could be also useful for attribution purposes, solving the so called back task of simulation (common in geochemical simulation of the origination of minerals), that is to find out the initial composition of the paint mixture given the chemical analysis of the aged sample. The manufacturers of art materials could also use the method to evaluate their products in various mixtures and environments. In general, the method could be of a real help in finding proper conditions of the accelerated aging. As concerns to the artists, its of a very low probability that Jackson Pollock would ever be willing to hear about any simulation program, but Rubens definitely might be interested to use it.

illustrations, and the paper in its new form was made available on the Cornell University Library site [13]. Current version contains some amendments as well as special updates for conservation professionals. The author is much obliged to the people of e_conservation magazine, whose attention, energy and help made this publication possible.

References
1. R. L. Feller, Accelerated Aging: Photochemical and Thermal Aspects, D. Berland, Ed. The Getty Conservation Institute, Los Angeles (1994) http://www.getty.edu/conservation/ publications/pdf_publications/aging.pdf, accessed on 20/10/2008 2. A Study of the Discoloration Products Found in White Lead Paint Films, http://aic.stanford.edu/sg/bpg/ annual/v04/bp04-04.html, accessed on 20/10/2008 3. Margriet van Eikema Hommes, Changing Pictures Discolouration in 15th to 17th Century Oil Paintings, Archetype (2004) 4. Blakey, R. R. Evaluation of paint durability - natural and accelerated. Progress in Organic Coatings 13:27996 (1985) 5. Cennini, Cennino, The Craftsman's Handbook http://www.archive.org/details/bookofartofcenni 00cennuoft, accessed on 20/10/2008 6. Odnoralov N. Materials in the Visual Arts. Moscow: Enlightment (1983), pp.144 7. ASTRA-4. Modeling of chemical and phase equilibria (manual). Moscow: MGTU (1991), pp.56

Acknowledgements The original preprint of this article, prepared in the main frame black-and-white computers era, was published in a small amount of copies by the Ministry of Culture of the USSR [12] with kind support of Dr. L. Gorelchenkova. Recently some results were calculated anew to allow for color
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8. Outokumpu HSC Chemistry. Finland: Outokumpu Research Oy, 2000, http://www.outotec.com/, accessed on 28/10/2008 9. Web Color Definitions. http://endprod.com/colors/, accessed on 28/10/2008 10. Color. Universal Language and Dictionary of Names, US Department of Commerce (1976)
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BORIS ZILBERGLEYT

11. Grenberg Y.I. Technique of painting. Moscow: Visual Arts (1982), pp. 539 12. B. Zilbergleyt, Simulation of the Chemical Aging of Painting with Computers, "Investigation of the Art Remnants, their Materials and Techniques", Moscow, Survey of the Ministry of Culture of the USSR (1989). 13. B. Zilbergleyt, Forecast of the Chemical Aging and Related Color Changes in Painting (2005) http://www.arXiv.org/physics/0505037.

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Photo I. Kresz

BORIS ZILBERGLEYT
System Dynamics Research Foundation Contact: sdrf@ameritech.net Boris Zilbergleyt, born in Ukraine, lived mostly in Russia and since 1991, in the USA. He has a bachelor's degree in Computer Science, a master's degree in Metallurgy and a PhD in Chemistry/Physical Chemistry. He worked as engineer and R&D scientist in the fields of Metallurgy, Chemical Engineering and Chemical Thermodynamics. His interests include research in discrete thermodynamics of chemical systems and painting materials. Currently he is affiliated with System Dynamics Research Foundation, Chicago, USA.
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case stud

RED MAITREYA TEMPLE LEH, LADAKH Mural Conservation Project

Part 2

A Tibet Heritage Fund Program

by Anca Nicolaescu and Andr Alexander

RED MAITREYA TEMPLE CONSERVATION PROJECT

Conservation Treatment The conservation project described in the previous number of the magazine had started in 2005 and is still ongoing. The whole project concept was built on the use of natural materials due to their compatibility with the original and availability in the area. Synthetic materials were used either in cases where the natural ones were inefficient or just for trials to be able to observe their results periodically for future investigations. Firstly preventive treatments for addressing the causes of damage or decay of the murals and the architectural systems they embellish were preferred. The THF team of architects, after extensive surveys and building analysis, found that the building is sound but that the parapets were badly disintegrated and the top soil and clay roof layers needed to be re-done.

Therefore, the first interventions were done on architecture structure in order to stabilize the conservation state of murals. The small roof above the Maitreya statue was restored; water spouts were replaced and improved and the roof parapets were extensively repaired using slate stone for water proofing. At the floor level the area from the north side of the ambulatory was temporary raised by layers of rubble stones in order to stop the water infiltration, the main cause for the original painting losses in that area. The stone layers do not transmit water and serve as a convenient walking ground to see the remaining paintings while performing circumambulation. For weathering protection the opening from the end of the north wall was closed (Figures 1, 2). The remedial interventions were based on systematic in situ research of materials and their behavior. Trials were done prior to any decision taken and extensive treatments were firstly done only on the most endangered areas where more losses of surface could have occurred otherwise. One of the initial tasks was to establish the real extent of the original paint surface which was covered with two and sometimes three different

Figures 1 and 2. For weathering protection the opening from the end of the north wall was closed.

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ANCA NICOLAESCU and ANDR ALEXANDER

plaster layers. Moreover the mortar used for the infilling of the gaps was overlapping the edges of the original painting. Based on the results of the stratigraphical trials done and recorded previously (Figure 3), the first interventions at the support layer began with the removal of the improper previous fillings, starting from the edges in order to protect the original surface and to avoid further losses of original support.

The mortar layers were removed one by one very carefully by mechanical means, starting with different types of scalpels, chisels or fiberglass sticks. In larger areas where the painted surface was stable a small hammer and chisel were used. After this intervention, mortar traces remained on the paint layer but they were left for further more specific cleaning operations.
Figure 3. Example of stratigraphic trial sheet made for identification of the mural painting edges on the west wall.

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RED MAITREYA TEMPLE CONSERVATION PROJECT

The most important interventions at the support level were the infilling of the gaps and consolidation of the detachments. Several testes were carried out in order to establish the suitable composition for mortar and grout, compatible with the original one. For fillings, the composition was based only on locally available materials: earth, sand, local clay (markalak1) and organic inclusions straws, same as used in the painting support (Figure 4). Observing the original existing mortars we set up the characteristics to be followed for the new material: - porosity; - mechanical resistance; - adhesive power; - workability; - linear shrinkage. For observation the mortars were applied on mud bricks or/and directly on the walls. The goal of the test phase was to choose the right composition, proportion and size of the ingredients in order to find a good material with similar physical-mechanical, plasticity and linear shrinkage characteristics. Two types of mortar were chosen; one rough for filling in the deep gaps of the support layer and a finer one for the final layer. The rough mortar composition was: sand 1p + gravel 1p + medium earth 4p + markalak 1p + straw, which mainly offered good mechanical qualities due the well-shaped grain size distribution of the aggregate, minimal shrinkage, good adhesive power, and a suitable hardness relative to the original plaster. From the workability point of view its coarse characteristics permit a thick layer application useful for deeper

Figure 4. The local materials used for mortars and injection grout.

gaps, avoiding the application of too many layers, which can lead to future damages. Moreover its rough texture enables better attachment for subsequent plaster layers. For the fine mortar the mixture chosen was: fine sieved sand 1p + fine sieved earth 2p + markalak 0,5p, which had very good adhesive power, cohesion and stability and at the same time a similar hardness and porosity to the original intonaco plaster. Beside its function of securing the area of the gaps, this last mortar layer should have an aesthetical impact on the final perception of the murals, thus the color and texture were factors in choosing its composition. The mortar was applied using spatulas or special trowels in successive layers leaving a sufficient time for drying (Figures 5-8).

1 Markalak is local clay consisting of 62% clay, 30%

calcium carbonate and 8% silt.

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Figure 5. Filling of the support gaps.

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Figures 6-8. Different stages during the filling of the support gaps with mortar.

The surface of the final layer of mortar which was part of the final aesthetical presentation was washed very carefully at the end with a special absorbing sponge in order to obtain an even and slightly rough aspect for both the aesthetical appearance and future interventions reasons (adherence of some other layers if necessary in some areas) (Figure 9).
Figure 10. Materials tested for the grout.

Figure 9. The final layer of mortar, applied under the original level of the painting was washed for obtaining a rough aspect.

For the consolidation of the support detachments different grout mixtures were tested for desired performance characteristics and working properties. The ingredients used in trials were: local materials - clay (markalak), yellow earth; different additional components as pumice, glass microspheres (Scotchilite K1), Casein, Acril 33, Syton X30 and small quantities of whipped egg white (Figure 10). Different types of grout have been injected for observations in mud bricks and sometimes
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original plaster fragments were grouted in situ to evaluate their adhesion (Figure 11, 12). Beside the compatibility of the grout with the original support which so far has been done only experimental in situ (further scientific and systematic research is required for an extensive treatment), another important selection criteria was the water quantity required by the respective composition. Having in mind the sensitivity to water of the original mural components, more water than necessary can be harmful for physical, chemical and mechanical reasons: dissolution, expansion/contraction, salt migration and risk of detachment can result. Also, yellow stains appear due to the organic materials from the support2 (Figure 13).

2 The appearance of the yellow stains was avoided by a thick

Japanese paper facing glued with Klucel G (hydroxypropyl cellulose) in ethanol. Thus the stain was remaining on the paper the evaporation was done at this paper level.
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Figure 11. The observation of different types of grout injected in mud bricks.

Figure 12. Tests for grout injection in mud bricks.

Figure 13. Organic components of the support can produce yellow stains on the original, this was avoided by using Japanese paper facing.

Two mixtures had good results so far after observing their behavior during the injection (fluidity and sedimentation) and after drying (retraction, cracking, adhesive power and water drop absorption): - yellow earth, markalak and Syton X30 3%: 10ml which was injected in small endangered area and had very good results from the adherence point of view (Figure 14); - yellow earth, markalak, pumice, Scotchilite and whippet egg white3.

For extended treatment it is important to be able to evaluate the results several months after the intervention and to re-orientate the method if necessary.
Figure 14. Consolidation of support small detachments.

3 From the available Getty Institutes literature regarding

organic materials in murals example of grout mixtures used in Dunghuan caves for support consolidation.
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Interventions at the paint layer level The main treatment problem at this level was posed by the overcoating layers which were covering the original. As mentioned in the conservation assessments, the paint layer being water sensitive and already damaged (flaking and powdering were occurring before the overcoat was applied), it suffered even more deteriorations during the over plastering due to both the very liquid application and perfect compatibility between the original and the overcoat layers. Thus the paint layer and the new plasters interacted forming a common mass which in some areas was almost impossible to separate. Particularly, the first overcoat layer (markalak) produced in time (or even from the beginning, during its drying process) grave damages due to a very good adherence, strapping the original which was more adherent to the overcoat than to the original support. Therefore, the treatments were combined, most of the time the removal of the overcoat layers being alternated with the fixation of the paint layer. Several materials and methods were tried in order to elaborate the best approach. Removal of the overcoat layers Following stratigraphical trials we determined that two main layers were covering the original: the first one in direct contact with the paint layer was a very uneven layer of markalak while the second was a thin white wash. The upper parts of the walls were covered only with the white wash. Removal of the white wash The white wash layer was very powdery and not adherent to the surface thus easy to be removed by soft brushes or very absorbent sponges wetted with a very small amount of water (Figure 15). However, the operation needs attention due to
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the detachments existing in the markalak layer. Also in the upper parts where this layer was applied directly on the powdering paint surface the removal was done carefully with dry cotton swabs. Removal of the markalak layer The removal of the markalak layer was the most difficult and time consuming task due to the wide range of damages on the original paint layer and the tight connection between the paint and the overcoat layers. Tests were carried out prior to the intervention for setting up the right methodology specific for each color, area or existing damage. Considering the paint layer's sensitivity to water, we used mainly dry mechanical methods (cotton swabs, different types of brushes, scalpels, fiber glass pencils, wishab sponges) (Figures 16-22).

Figures 15 and 16. Removal of the white wash (upper) and of the markalak layer (lower).
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Figures 17-22. Different cleaning methods used simultaneosly or according to the state of the paint layer: hard brush for the markalak layer (upper left), dry cotton swabs or moisted with isopropyl (upper right), cotton swabs used in parallel with soft brush (middle left), cotton swabs with scalpel (middle right), eraser (lower left) and aspect of the area after cleaning (lower right).
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Where the markalak was very thick or uneven applied, the area was first thinned until an even thin layer was obtained so that the paint layer underneath could be easier controlled and checked. We tried to improve the results of the dry mechanical method using in parallel chemical cleaning. Several solvent mixtures were tried but the best results were obtained with isopropyl alcohol used in powder cellulose poultry (Arbocel BC 200) applied on the markalak layer. The markalak became more powdery this way and easier to remove without affecting the sensitive paint layer. This solution however was not possible to use on areas with detachments or flaking colors. Depending on the colors, their conservation condition and behavior during the tests, different techniques and tools were used in parallel (Figures 23-28) For a better view of the treatment results in connection with color, damages and methods, our observations for each color behavior and cleaning technique were gathered (see Table 1).

Figures 23-26. Different aspects during the cleaning of the overcoating layers.

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Figures 27 and 28. Different aspects during the cleaning of the overplasters.
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Color Location

Technical details
Thin and compact layer Applied in a thin layer on the ornaments

Condition

Behavior during cleaning

Very good

Method used Observations

Black

Contour drawings, figures Flowers, jewelry, figures Ornaments, flowers

Stable; small losses that occurred before the markalak was applied Very adherent to the markalak layer

Scalpels, brushes, cotton swabs; alcohol+ water (2:1) Soft brushes, cotton swabs

Very resistant

White

Very sensitive

Difficult to recover; weak adhesion to the background; consolidation necessary during cleaning Good results; crust can break at the use of the scalpel; time consuming operation

Earth green

Applied thicker; Mostly flaking; still absorbed by the stable due to its ground connection with the surrounding colors Separated in layers, one layer connected to markalak; crust; damaged before the overcoating Damaged before the markalak (technical deficiency); flaking in some areas; powdering (upper part) Powdering

Good on Soft brushes, compact cotton swabs, surfaces; wishab flaking areas

Bluegreen

Background, Thick layer sky, ornaments, lotus Applied on 2 layers: a very thin preparation layer (fire) and a ticker one (ornaments)

Cold red Background, figures, clouds, hands, mandalas

Very good; powdering due to water leaks (upper part) Sensitive Cotton swabs; smooth brushes

General good condition; areas where a thin layer remained on the surface were cleaned by brushing; consolidation with fish glue afterward Consolidation is needed afterward

Warm red Deities hair, Very opaque; good covering - orange clothes power Orange Ornaments, Thick layer, less background, binder clothes, underlines Pink Some ornaments, underlayers Very thin layer

Powdery; weak adhe- Sensitive sion; very adherent dirt; damaged before the overcoating Washed out

Cotton swabs, General good condition. scalpel, Consolidation is needed fiberglass sticks. afterward Very difficult removal of markalak Very difficult removal of markalak; consolidation during the cleaning Very difficult, several trials of consolidation during cleaning

Difficult due Cotton swabs to its thinness Cotton swabs, fiberglass sticks

Purple Lotus flower Thin layer on Clothes white Clouds Dark blue Very thick layer, absorbent, hard, matte aspect

Seriously damaged Difficult before the markalak; flaking; strapped in some areas Poor condition, flaking, strapped by the markalak; Damaged before the overcoating Among the most difficult to clean

Soft brushes Cotton swabs

Light blue

First Very thin layer, Seriously damaged Very difficult Soft brushes platform, absorbed by the before the markalak; Cotton swabs Gurgon deity preparation strapped layer Lotus flower, Thin layer Clouds, Snakes Traces in some areas Stable on the snakes Generally and ornaments. Con- stable nected to the markalak in some areas Instable, powdering Difficult Compresses with isopropyl; fiberglass stick

Parts of the fine grey details were saved. Consolidation during the cleaning

Grey

Yellow

It was applied as underpaint layer for the gilded areas

Table 1. Observations during the cleaning of the west wall (first years intervention). Other recordings were added later.
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We found this useful for both correlating the damages and the appropriate approaches as well as for future research regarding this issue. During this process the paint layer was fixated simultaneously or/and consecutively using different methodologies further described. After the entire area was already consolidated a last cleaning was done by the mean of wishab sponges in order to remove the white veil which remained from the markalak dust. Fixation of the paint layer The fixation of the paint layer was imperative due to the high degradation level which would definitively have led to large losses. On the other hand, this operation implied the use of a fixative material which, if its choice is not based on sufficient research regarding the original materials, damages and effects, could produce undesirable consequences in the future, leading even to grave changes of the initial proprieties and conservation condition of the original. Therefore we chose animal glue as fixative, which is very compatible with the original (knowing that the original binding agent was animal glue), avoiding thereby unexpected future reactions. After checking the local animal glue used as binder even nowadays we decided that its level of chemic
Figure 29. Fixation of the color by spraying fish glue.

impurity (color and unknown particles) could affect the original. Therefore it was decided to use the fish glue injected or sprayed depending on the damages type (powdering or flaking paint layer). Some other fixatives were used but only in areas where the animal glue was not effective or in trials for future observations and research, being aware that future investigations and periodic evaluations of the results are needed in order to re-orient the method if necessary. Thus, the different materials and methods used according with the damages necessities were: Fish glue (2-4%) For the powdering areas the warm glue was sprayed (Figure 29) on the surface. Depending on the absorption level of the paint layer some alcohol was sprayed before for a better penetration. After the fixative was totally absorbed by the paint layer the surface was gently pressed with a special rubber roller over a layer of Japanese paper and a layer of polyester foil (melinex) applied as protection (Figure 30). Observing the behavious of the surface after the treatment, sometimes the operation was repeated. Very good results were obtained with this method the adherence was reestablished and the original paint aspect preserved (Figures 31, 32).
Figure 30. Pressing of the paint layer.

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Figures 31and 32. Before and after the fixation treatment of the paint layer.

For a better control of the penetration of the glue into the big flaking areas it was seen that injected fish glue gives very good results. This approach was used for some areas, the methodology afterwards being the same as described above. For consolidating the paint layer strapped by the markalak the warm fish glue was injected in the

damaged area (Figure 33) then the surface was laid down on the support by means of a spatula or special rubber roller (Fgure 34). The adherence of the paint to the support was resolved in this way but the markalak layer became harder to remove as the glue was absorbed by the markalak layer and thus the paint layer could have suffered damages during the cleaning (Figure 35). Therefore more trials with different materials were required for obtaining better results. Paraloid B72 (5% in acetone) Trials were also done with Paraloid B72 for consolidating the paint layer strapped by the markalak. Japanese paper facing with CMC was applied on the markalak and the detachment was opened.

Figures 33 - 35. Paint layer consolidation.

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Paraloid 5% in acetone was applied on both the back of the strapped paint film remained on the markalak and on the support area from where the paint layer was strapped (Figure 36). When the Paraloid was dry, acetone was brushed on the support surface in order to reactivate it and the strapped fragment was pressed back on the support using a special rubber rolle (Figure 37). After the perfect drying of the surface, the facing was removed by wet cotton swabs and the markalak was removed mechanically or with a mixture of water isopropyl (Figures 38, 39). This method had good results but only where the paint layer was compactly strapped by the markalak and not very connected to it. The fixed paint layer suffered no changes in its original matte aspect. For areas where only small fragments of the original color were strapped the method did not work due to both the difficulty of applying Paraloid on small support lacunae (from where the color was strapped) and the fast evaporation rate of the acetone (not enough time to be applied on all of the fragments without getting dry or over touching the surrounding areas). Further research will be useful for finding an efficient solution for this specific paint layer deterioration. Rabbit glue (4%) In the areas where the paint layer was detached together with parts from the preparatory layer, the rabbit glue was more appropriate to use due to both its better adhesive power and its capacity of creating a thin layer which could provide a better ground for pasting of thick layers. The warm glue was injected in the detachment area and pressed with a spatula or a special rubber roller over a melinex foil. In the areas where part of the support was lost and the paint layer had nothing to lay on we used as filler (before fixing the paint) sieved
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Figures 36-39. Fixation of the paint layer with Paraloid.

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Figures 40-42. Different aspects during the consolidation of the paint layer with rabbit glue.

earth in mixture with rabbit glue which was applied by spatulas. Very good results were obtained with this method, the paint layer becoming stable. Cleaning Beside the removal of the over-plasters and the mechanical cleaning with the wishab sponge as described above, several cleaning trials were done in the lower part of the west wall (on the donors frieze) were dust and soot had altered the original aspect of the murals due to the use of the butter lamps.
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Trials were carried out with different solvent mixtures: - acetone alcohol (1:1) the dust and remains from the over-plaster removal were satisfactorily cleaned; - acetone - isopropyl (1:1) better results; - isopropyl in cellulose paste poultry (Arbocel) good results; - isopropyl in Japanese and napkins poultry pressed with a rubber roller very good results. Very good results were also obtained by mechanical means, using fiberglass sticks of different thicknesses. Considerations regarding the final aesthetical presentation of the paintings The temple, still regularly used for ritual purposes, it is not preserved as historic monument but as a living and active even interactive space between art, spirituality and those people who step inside it. From this reason an intervention strategy was established for choosing an appropriate final presentation, able to eliminate the divergences
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between the correct chromatic retouching without creating a fake and the recovery of the integrity of the art work demanded by its religious function. First of all, the lacunae were classified from two points of view: stratigraphically, categorizing them due to the level where they appeared: erosions of the paint layer (irregularities of the paint hue due to some slightly mechanical damages or chemical alteration), lacunae in the paint layer (losses of the paint layer), superficial support lacunae (losses of the support at the intonaco level) and deep lacunae of the support layer (losses of the support at the arriccio level). From the image perception point of view lacunae were divided in several types: lacunae that can be integrated (erosions of the paint layer), lacunae which can be integrated by a reconstructive process (they must be of small dimensions and located in areas which preserve enough original elements) and large lacuna fields which cannot be retouched.

This simple organization of the damages was helpful for setting up a retouching methodology where same types of lacunae were to be treated in similar way on the whole ensemble for obtaining a final unity. Another aspect of the retouching stage was choosing the right media to be used for preserving the original matte aspect and being reversible as much as possible. Two types of materials were tried: pastels, which are very easy to remove and mineral pigments using as binder Klucel G in alcohol 2% (Figure 43). Pastels, besides having a good reversibility which sometimes could have been a disadvantage (in the lower part where the painting can be easily touched by visitors) were not easy to apply on small lacunae without touching the original.
Figure 43. Retouching tests with pastels (left) and pigments with binder (right).

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Figure 44. Ensemble before chromatic reintegration.

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Even though the area retouched using pastel was reaching a good chromatic aspect, this methodology was impossible to use on all types of lacunae. The trials done with Klucel G as binder and mineral pigments gave very good results: easy to be applied even on very small erosions and in same time very reversible with alcohol which is not affecting the water sensitive original murals. Having chosen the materials to be used, the retouching techniques were selected depending on the nature of the lacunae. The very small and superficial ones were integrated with a light glaze which permits the recovering of the surface evenness without the alteration of the rest of the paint layer (Figure 45-48). Retouching the lacunae of the paint layer that were disturbing the image not only due to surface alteration but also due to the small white or light
Figures 45 and 46. Chromatic reintegration by velatura.

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Figures 47 and 48. Before and after chromatic reintegration.

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Figure 49. Chromatic reintegration of the paint layer. Figure 50. Chromatic reintegration by tratteggio.

colors of the appearing support was done by means of transparent glazes (velatura) applied in dots using neutrals colors. As a result, the white spots of the paint gaps were optically pushed backwards leaving the original readable. The reconstructive method used for the superficial support gaps was the hatching technique (tratteggio) using watercolors this time because the retouching was done on new support, able to be removed if necessary. Community integration into the conservation project Before THFs project, there has been not a single Ladakhi restorer. Conservation projects in the region always involved only foreign or Indian mainland experts. Therefore, the involvement and training of locals was an important aspect of the project.
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Figure 51. Before chromatic reintegration of the paint layer.

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Figure 52, 53. Chromatic reintegration of the paint layer.

The two most promising students have completed an internship in Germany at the conservation laboratories of Erfurt University of Applied Science in May - July 2007. These two and other trainees will participate in the project to gain further training. They have already gained good knowledge and skills regarding conservation issues and respect of heritage authenticity and thus, hopefully, they will be able to maintain their valuable heritage in the future. Conclusion What we had presented in this paper are all our experimental interventions and trials which must be re-evaluated regularly and followed by more systematic researches. That is the reason why the needed extensive treatments were done only with glue instead of the local animal glue, avoiding hence uncontrollable future damages.
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ANCA NICOLAESCU and ANDR ALEXANDER

At the end of this project, murals from the first half of 15th century were recovered in Red Maitreya, being now the oldest extant paintings in Leh. Several key historic sites in Ladakh preserve comparable historic art, but almost all of them require urgent conservation intervention. Many have been lost in the past 2 decades. The investigation of the paintings in the Red Maitreya Temple of Leh has allowed first conclusions as to the technologies and conservational challenges of early Western Himalayan hoping that questions have been raised for future investigations. Acknowledgments:
We wish to thank to the project sponsors Trace Foundation New York and InWent Germany; Erfurt University of Applied Sciences Germany for their cooperation which made the project possible thorough students volunteering (Hanna Pohle, Derya Pektas, Jana Bulir, Olga Emgrund, Sonia Cabela, Anke Farnik, Rebekka Ewert and Jovanna Gla) and their professor Meinhart Landmann; and to the devoted local trainees Jangchen Dolma and Skarma Lotus. The National Research Laboratory for Conservation and Restoration of National Cultural Heritage (LNC) Romania especially to Prof. Gheorghe Niculescu Director of LNC and his team (Dr. Olimpia Hinamasuri Barbu and Dr. Georgescu Migdonia) for all the scientific research presented here.

ANCA NICOLAESCU
Contact: ancanicolaescu@yahoo.com Anca Nicolaescu is a Romanian mural painting conservator with Master degree from the University of Fine Arts Bucharest, ConservationRestoration of art works department. She received recognition as specialist from the Romanian Ministry of Culture in 2005 after having coordinated various distinguished conservation projects. One of the projects (a 17th century mural painting ensemble) done by Restauro Art Grup (the conservation enterprise where she is a co-founder) was awarded in 2004 the "Vasile Dragut" prize for Cultural National Heritage by the Romanian Ministry of Culture. Her work experience includes international participation at conservation projects and seminars in UK, Turkey, Uzbekistan, Japan and India.

ANDR ALEXANDER
Contact: info@tibetheritagefund.org Andr Alexander was born in West-Berlin in the Year of the Wood Dragon. He currently divides his time between Ladakh, China and Germany. He was trained by traditional master craftsmen in Lhasa in traditional Tibetan architecture, and is currently affiliated with Berlin University of Technology (MSc in Urban Management and PhD candidate in Architecture), where he occasionally lectures. He is co-founder and first chairman of Tibet Heritage Fund, an international non-profit organisation working to preserve the heritage of the Himalayan regions. He has a prodigious publishing activity, from which several articles and reports can be seen online on THF's website.

References:
1. Stephanie Bogin, A technical Study of the early Buddhist wall paintings at Nako, India, Unpublished Masters thesis, Courtauld Institute of Art (2004) 2. David Jackson and Janice Jackson, Tibetan Thangka Painting: methods and materials, Snow Lion Publications, New York (1988) 3. Ann Shaftel, "Note on the technique of Tibetan Thangkas", Journal of the American Institute for Conservation, 25 (1), (1986) pp. 97-103 4. Leslie Rainer and Angelyn B. Rivera (ed.), The conservation of decorated surfaces on Earthen Architecture, Getty Publications (2006) 5. Gernot Minke, Building with earth design and technology of a sustainable architecture, Germany, Birkhauser Basel (2006)

THF - TIBET HERITAGE FUND

www.tibetheritagefung.org
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CONSERVATION OF PLASTICS
Materials Science, Degradation and Preservation
Review by Brenda Keneghan

Author: Yvonne Shashoua Publisher: Butterworth-Heinemann Publication Year: 2008 Pages: 300 ISBN 13: 978-0-7506-6495-0 ISBN 10: 0-7506-6495-9 Language: English List Price: 49.99 (72.95)

The degradation of plastic objects in collections has been a growing problem for museums and galleries over the last 20 years; their sudden and spectacular disintegration confounding conservators more familiar with dealing with the gradual decline of traditional materials. As plastic has become ever more ubiquitous this problem is set to escalate. The 1991 CCI conference Saving the Twentieth Century started the ball rolling on international discussions and a great variety of case histories have been presented at conferences over the intervening years. On the publications front Anita Quyes & Colin Williamsons Plastics: Collecting and Conserving (1999), immediately springs to mind as a turning point on the subject. But this excellent little book is almost 10 years old and is targeted towards a general audience: the amateur collector as well as the museum professional. There has been a distinct gap in the literature on this subject ever since. Now Yvonne Shashouas Conservation of Plastics, has come along and filled that gap in a most clear and comprehensive manner. The book is a welcome addition to the Butterworth-Heinemann series
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of conservation and museology publications, and continues the same high standards. Yvonne Shashoua is eminently qualified to compile such a book, having specialised in modern materials conservation for several years in the British Museum before moving to the National Museum of Denmark to undertake PhD research work into the degradation of PVC. Her (2001) PhD thesis, 'Inhibiting the deterioration of plasticized poly (vinyl chloride) a museum perspective' has become a cornerstone in conservation science literature, applying rigorous science to a practical heritage problem. A major problem with the conservation of plastics is that a certain knowledge of chemistry is required before attempting either an interventive or inhibitive (Yvonnes preferred term) treatment. This book is intended to appeal to a wide readership, including practical conservation students and practitioners as

book revie

BOOK REVIEW

well as conservation scientists. This is a tough target to meet without frustrating or disappointing someone, but the structure of the book facilitates the gradual introduction of technological and chemical principles in a neither an over-simplistic nor patronising manner. Each chapter is preceded by a very useful summary of its contents allowing the reader to decide whether they wish to go more fully into this area or not. Almost by way of a summary, Chapter 1 tells us where plastics are found in collections and finishes with a brief word on the current status of plastic conservation. The following three chapters form a complete introduction to plastics, beginning appropriately with their historical development (Chapter 2) and followed by their technological production (Chapter 3) and their properties (Chapter 4). Each of these three chapters is illustrated with attractive colour photographic images and extremely comprehensive tables. In fact, the quality and content of the images and tables throughout the book is exceptionally high. Chapter 3 introduces the chemical structures of monomers and describes the polymerisation processes and resulting polymers in the most painless manner possible. The different types of polymerisation reactions are described. There is also an extremely useful table (Table 3.3) summarising the types, functions and examples of frequently used additives. These tables are a most valuable resource for both the newcomer to the field and those more experienced. The chapter ends with descriptions of the various industrial processes by which the plastics are transformed from granules or liquids into various types of everyday objects. Chapter 4 presents an overview of the chemical, optical and thermal properties of plastics which are most relevant to conservation. Chapters 5, 6 &7 (identification, degradation & conservation) are, perhaps, the chapters that non-scientists will immediately turn
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Example of plastics cleaning treatment, discussed in Chapter 7. Dirt deposits on the surface of a polyurethane foam shark model used in the Jaws films were mechanically cleaned to improve its appearance.

to when first confronted with a degrading plastic object. Identification by means of various tests, e.g. hot pin, density, burn tests and solubility are described (along with warnings as to their dangers). Chemical spot tests are also described as giving rapid identification, however never having had any success with these myself, I must disagree
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BOOK REVIEW

with this statement. The chapter concludes with a description of the various types of instrumental analysis useful for polymer identification. The opening sentence of the summary to Chapter 6 states "It is essential to understand the factors causing degradation prior to developing an approach to the conservation of plastics". This is probably the most important sentence in the entire book as experience has shown that the "conservation" of plastics cannot be tackled in the same manner as the conservation of more traditional materials. This is due to differences in chemical composition of individual plastics and/or combinations of different factors being responsible for their degradation. Chapter 6 describes in detail the degradation pathways of the four most problematic plastics in museum collections: cellulose nitrate, cellulose acetate, plasticised PVC and polyurethane foam. Table 6.2 charts clearly and comprehensively the effects of radiation, heat, oxygen and water on the major plastics found in collections. Again this is a most useful resource. Photographic illustrations of the results of physical and chemical degradation bring the message home. Chapter 7 follows on logically from Chapter 6 by describing current practice in the conservation of plastics - inhibitive and interventive. The scientific principles behind the use of various adsorbents and scavengers are explained. Hopefully, this will put an end to repeated recommendations for the inappropriate use of Ageless that have been heard over the previous few years. The pros and cons of low temperature storage are outlined and explained. The cautious approach that has been adopted towards the seemingly simple procedures such as cleaning and adhering plastics is explained and supported by tables of solubility parameters and surface tension values for solvents and plastics. Having said this, the interventive treatments that have been attempted are also described or refere_conser vation

enced. Finally, Chapter 8 looks forward to the future of plastics conservation and suggests that a way forward might be to develop an information interface between manufacturers and users as well as increased specialised training. The main text is supplemented by three appendices including a very useful mini-dictionary of degradation terms (with accompanying photographic images). In summary, the book is very clearly and thoughtfully laid out. An enormous amount of painstaking work has gone into sourcing the information from both the scientific and conservation literature and presenting it in such an accessible manner. It is well illustrated with tables and photographic examples. The references at the end of each chapter are comprehensive and up to date. Conservation of Plastics does not teach one how to conserve plastics but it does provide a background that will enable a conservator or conservation student to make informed decisions on the advisability of potential treatments. By providing information previously difficult to obtain in a readily accessible format perhaps more interventive treatments will be attempted. Yvonne states in the introduction that the purpose of the book is "to distil the extensive knowledge produced by the polymer and plastics industries, designers, environmental and conservation professionals into a single publication focussing on the preservation and conservation of plastics". I think she has succeeded beyond expectation in this mammoth task.

Reviewed by Brenda Keneghan, Polymer Scientist Conservation Department - Victoria & Albert Museum London SW7 2RL
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No. 7, October 2008 LICENCE ISSN: 1646-9283 Registration Number Attribution-Noncommercial-No Derivative Works 2.5
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Photo by Anca Dina Detail of the stone inscription from the church of Voronet Monastery (1488)

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