This document summarizes research conducted on a late 16th century German house altar with seven reverse glass paintings prior to its conservation treatment. Technical examination of the glass substrates and painting technique revealed the panels were likely made via the cylinder blowing process. Scientific analysis identified the binding medium as heat-treated pine resin modified with softening resins. Red paint contained cochineal and dragons blood, while original blue and green areas contained smalt and copper resinate but had undergone color change. Prior to treatment, the detached and fractured paint layers were reattached to the glass. However, discoloration in the blue and green areas remained.
This document summarizes research conducted on a late 16th century German house altar with seven reverse glass paintings prior to its conservation treatment. Technical examination of the glass substrates and painting technique revealed the panels were likely made via the cylinder blowing process. Scientific analysis identified the binding medium as heat-treated pine resin modified with softening resins. Red paint contained cochineal and dragons blood, while original blue and green areas contained smalt and copper resinate but had undergone color change. Prior to treatment, the detached and fractured paint layers were reattached to the glass. However, discoloration in the blue and green areas remained.
Original Description:
art conservation
Original Title
Conservation and Research of Reverse Paintings on Glass
This document summarizes research conducted on a late 16th century German house altar with seven reverse glass paintings prior to its conservation treatment. Technical examination of the glass substrates and painting technique revealed the panels were likely made via the cylinder blowing process. Scientific analysis identified the binding medium as heat-treated pine resin modified with softening resins. Red paint contained cochineal and dragons blood, while original blue and green areas contained smalt and copper resinate but had undergone color change. Prior to treatment, the detached and fractured paint layers were reattached to the glass. However, discoloration in the blue and green areas remained.
This document summarizes research conducted on a late 16th century German house altar with seven reverse glass paintings prior to its conservation treatment. Technical examination of the glass substrates and painting technique revealed the panels were likely made via the cylinder blowing process. Scientific analysis identified the binding medium as heat-treated pine resin modified with softening resins. Red paint contained cochineal and dragons blood, while original blue and green areas contained smalt and copper resinate but had undergone color change. Prior to treatment, the detached and fractured paint layers were reattached to the glass. However, discoloration in the blue and green areas remained.
The document discusses the conservation of a German house altar from the 16th century with reverse paintings on glass. Various scientific analyses were conducted to study the materials and inform the conservation treatment.
Gas chromatography–mass spectrometry, amino acid analysis, high performance liquid chromatography, micro X-ray fluorescence spectrometry and scanning electron microscopy with energy dispersive X-ray microanalysis were used to analyze the materials.
The main component of the binder was identified as heat-treated pine resin (colophony), modified with various softening resins.
Maney Publishing and International Institute for Conservation of Historic and Artistic Works are collaborating with
JSTOR to digitize, preserve and extend access to Studies in Conservation.
http://www.jstor.org Maney Publishing A German House Altar from the Sixteenth Century: CONSERVATION AND RESEARCH OF REVERSE PAINTINGS ON GLASS Author(s): Simone Bretz, Ursula Baumer, Heike Stege, Johannes von Miller and Dedo von Kerssenbrock-Krosigk Source: Studies in Conservation, Vol. 53, No. 4 (2008), pp. 209-224 Published by: on behalf of the Maney Publishing International Institute for Conservation of Historic and Artistic Works Stable URL: http://www.jstor.org/stable/27867045 Accessed: 18-08-2014 08:48 UTC Your use of the JSTOR archive indicates your acceptance of the Terms & Conditions of Use, available at http://www.jstor.org/page/info/about/policies/terms.jsp JSTOR is a not-for-profit service that helps scholars, researchers, and students discover, use, and build upon a wide range of content in a trusted digital archive. We use information technology and tools to increase productivity and facilitate new forms of scholarship. For more information about JSTOR, please contact support@jstor.org. This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 209 A German House Altar from the Sixteenth Century CONSERVATION AND RESEARCH OF REVERSE PAINTINGS ON GLASS Simone Bretz, Ursula Baumer, Heike Stege, Johannes von Miller and Dedo von Kerssenbrock-Krosigk Prior to the conservation treatment of a late sixteenth-century South-German house altar with seven reverse paintings on glass, technical and scientific research was conducted on the glass substrate, binding media, colourants and metals. Microscopic examination revealed the particularities of the so-called amelierung technique and the glass panel manufacture. For material analysis, gas chromatography?mass spectrometry, amino acid analysis, high performance liquid chromatography, as well as micro X-ray fluorescence spectrometry and scanning electron microscopy with energy dispersive X-ray microanalysis were applied. The main component of the binder was identified as a heat-treated pine resin (colophony), modified with various softening resins. The red paint layer contains cochineal and small amounts of dragons blood. The original blue and green areas, which contain smalt and copper resinate, have undergone considerable colour change. The reverse paintings on glass were in a poor state of preservation: due to high moisture (flooding at the museum) and material degradation, the paint layers were severely delaminated, fractured into hundreds of small paint flakes and partially attached to silverfoil and paper backing The detached paint flakes were transferred back to their original positions on the glass with a fine brush and secured using a hydrocarbon resin. This was followed by the application of microcrystalline wax which achieved a brilliant saturation of the reverse paintings on glass. However, the discolouration remained in the blue and green areas. A photograph of the altar's central panel after the conservation treatment was digitally manipulated to recreate the presumed original tonality. INTRODUCTION Almost 40 years went by from the time of the acquisition of a small house altar by the Corning Museum of Glass in 1959 until its permanent display in the museum's galleries. A conservation treatment grant approved by the Getty Foundation made it possible to exhibit this masterpiece of Renaissance reverse painting on glass (Figure 1). The poor preservation condition and severe damage prompted a preliminary study of the technology and materials of the altar's reverse paintings on glass. This delicate and fascinating painting technique, called amelierung, has been the subject of technological research, which was published by Ryser and Bretz in several monographs, papers and contributions to exhibition catalogues [1?6]. Scientific analysis of colourants and binding media of reverse paintings on glass has been carried out by Hahn [7] and by Koller and Baumer [8], but more work is required to allow broader comparisons between periods or regions to be made. Regarding the actual state of the art in conservation on reverse Received February 2008 paintings on glass, Bretz published an overview on restoration treatments of the past 20 years [9]. This paper presents a summary of findings on the technique and materials used for the Corning house altar with special emphasis on the reverse paintings on glass. Stereomicroscopy was used to examine closely the painting technique and to document the state of preservation of the paintings. Various spectroscopic and Chromatographie methods were used for the analysis of glass panels, metals, colourants and binding media.. The results of the analysis contributed to a better understanding of colour changes and allowed the appropriate choice of conservation materials to be made. A description of the conservation/restoration treatment and its difficulties is given. The analytical and conservation efforts yielded enough information for a virtual reconstruction of the original appearance of one of the reverse paintings on glass. DESCRIPTION OF THE HOUSE ALTAR The house altar from the Corning Museum of Glass (acc. no. 59.3.39) is made of an ebony-veneered oak case STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 210 S. BRETZ, U. BAUMER, H. STEGE, J. VON MILLER AND D. VON KERSSENBROCK-KROSIGK Figure 1 House altar with reverse paintings on glass, Corning Museum of Glass (59.3.39), after conservation. ? Corning Museum of Glass, Corning (NY). and is decorated with seven reverse painting on glass panels (Figure 1). It originates from South Germany, perhaps Nuremberg or Augsburg, and probably dates from around 1560-1580. The central panel shows the Crucifixion, with St Mary, St John, and probably Mary Magdalene (Figure 2). The wings, when open, depict the allegorical figures Pity and Charity, bearing the inscriptions 'MISERICORDI' and 'CHARITAS' respectively. The wings, when closed, display St Bridget and St Dorothy, with the inscriptions 'S. PRIGIDA' and 'S. DOROTHEA'. The oval panel on the pedestal represents the Seven Sorrows of the Virgin in a medallion: Figure 2 Crucifixion after treatment. ? Simone Bretz, Munich. the Virgin Mary, with seven swords pointing toward her. The panel in the lower niche shows the Virgin as Queen of Heaven, holding the Christ Child. The back of the altar is flat. The dimensions of the house altar are: height 49.6 cm; width with wings closed 19.5 cm; depth 12.7 cm. House altars (i.e., altars used for private devotion) with reverse paintings on glass are not rare. An altar of this kind in the Bayerisches Nationalmuseum in Munich, Germany (acc. no. R 1104) shows the Coronation of the Virgin Mary, surrounded by other scenes related to Mary: the Seven Sorrows, the Piet?, the Flight into Egypt, and the Assumption [10, pp. 59-60, fig. 14]. The artist followed closely a print by Johannes Sadeler after a composition by Marten de Vos [10, p. 58, fig. 12]. The altar is 37 cm high; its wings are not movable. A second comparable altar, showing the Assumption of the Virgin Mary with St Jerome, St Ambrose, St Gregory and St Augustine, STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions A GERMAN HOUSE ALTAR FROM THE SIXTEENTH CENTURY 211 is in the Museo Civico in Turin, Italy (acc. no. V.O. 48 2941), and has a height of 39 cm [11]. A third altar is in the National Museum in Cracow, Poland (acc. no. MNK XIII-2324).The case is made of ebony-veneered pinewood (height 44 cm), and the central panel shows the Nativity, with the Annunciation and the Adoration of the Magi on the side panels. These three altars also originate from South Germany and date from the late sixteenth or early seventeenth century. Of these three altars, the Cracow altar most closely resembles the Corning piece. Both have wings that are hinged on the columns in a very sophisticated way. Also, the general configuration, with a drawer at the bottom, is the same. TECHNICAL EXAMINATION Glass manufacture The technique by which the glass panels of the house altar were made is as yet not entirely understood. The glass is very glossy and thin (between 1.7 and 3 mm) and slightly uneven, which makes it unlikely that the panels were cast and polished. The presence of mostly perfectly spherical and only a few oval air bubbles in the glass indicate that the panels were made by the cylinder blowing process [5, pp. 189-190]. Judging from the length of the oval bubbles, the cylinder must have been short, otherwise the bubbles would have been more elongated due to lengthening of the hot glass cylinder during blowing. Once the cylinder had been cut along its length and allowed to flatten, the panels were cut to size. Amelierung technique Well-executed reverse paintings on glass do not reveal the complexity of their manufacture. Since the design is applied to the back of glass panels, the painting must be built up in reverse order, starting with the details and foreground and working 'backwards'. This technique makes corrections virtually impossible. Reverse paintings on glass are known under the German term hinterglasmalerei in many countries. If the technique makes use of gold and silver leaf applied to the glass, the painting is often referred to as verre ?glomis?. However, in the case of the house altar, the German term amelierung (or gamalierung) is more appropriate. The term is not translatable but in old German gamal means colourfully decorated. This speciality had been introduced in Nuremberg, Germany, before 1532 by applying metal leaf and/or metal powder (both gold and/or silver) onto the glass panel, after which the decoration was etched with a needle or stylus [5, pp. 196-201]. A second layer of colourful translucent lacquers (lustre) was then applied and covered with a layer of silvery foil (silver or tin), creating sparkle and luminosity. In the case of the house altar a thin silver foil was attached to paper, which was then glued to the edges of the glass panel. In addition to the technique of amelierung, the altar shows a special treatment of the flesh layer, consisting of silver powder and pigments that were painted on, engraved afterwards and highlighted by applying black paint. Delamination of paint layers The most typical disfigurement occurring on reverse paintings on glass, which was also observed on the house Figure 3 Crucifixion before treatment. ? Corning Museum of Qlass, Corning (NY). STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 212 S. BRETZ, U. BAUMER, H. STEGE, J. VON MILLER AND D. VON KERSSENBROCK-KROSIGK Figure 4 Detail of Virgin as Queen of Heaven, showing delamination, cupping and loss of paint. ? Simone Bretz, Munich. altar, is the separation of paint from the glass, which when seen from the front appears as patches of greyish, less saturated areas of paint. An estimated 80-90% of the paint surface of the house altar was no longer securely attached to the glass substrate (Figures 3 and 4). Hundreds of small, dislodged paint flakes and splinters were loose and needed to be reintegrated.Various factors like normal ageing mechanisms under the influence of changing climate conditions caused brittleness, flaking and resulting glass-like paint fragments. Degradation processes were further aggravated when the Corning Museum of Glass was inundated during a flood in 1972. Lastly, heat, perhaps from accelerated drying after the flood, had caused softening and fusing of some of the paint layers. The glass itself was found to be in good condition and showed no signs of degradation like crizzling. In general, a reverse painting on glass comprises a non-porous glass substrate and a multi-layered paint system. Internal and external factors influence the degradation. A cleaned, degreased glass surface and a well-chosen binding medium are crucial factors for good physical bonding at the paint/glass interface. Poor surface wetting produces voids that restrict contact and trap air. The level of adhesion of the paint layer to the glass support depends also on the composition of the paint (colourants and binding media) and its drying mechanism, the process of film formation and the method of application. The brittleness or flexibility of the organic coating is in correlation with the thickness of application: the thicker a paint layer, the more prone it is to delamination. The instability can also be caused by a warm environment that results in faster volatilization of the solvent and softeners. With changes in temperature and, as consequence, changes in relative humidity, the paint film takes up and releases moisture. The stress of shrinking and expanding will lead to hairline cracks and voids within the paint matrix, to blistering and cupping, and ultimately to the loss of paint fragments. MATERIAL ANALYSIS Glass To avoid taking samples from the undamaged glass, a semi-quantitative, and for some elements qualitative determination of the glass composition was undertaken by energy dispersive micro X-ray fluorescence spectro metry ^XRF). Six of the seven panels were examined after local cleaning with ethanol/water, but without additional polishing, thus taking into account that values obtained for light elements, mainly sodium to silicon, are affected by leaching processes. The six panels showed a very similar composition with only small variations. In general, the glass is rich in potassium (~ 16-17 wt% K20) with medium calcium content (~ 8-10% CaO) and only traces of lead. In addition, the absence of bromine in the spectra proves that ash from halophytic, soda-rich plants can be excluded as the fluxing agent. Using a similar spectrometer type, M?ller was able to show that traces of bromine can be regarded as a characteristic marker for soda ash glasses [12, p. 122]. The ratio of K90/CaO in the glass panels was found to be around 1.7 to 2.0 and therefore at the upper limit for so-called 'colourless wood ash glasses', a modified typification suggested by M?ller [12] following the chemical classification of medieval glass by Wedepohl [13]. However, a partial addition of purified wood ash STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions A GERMAN HOUSE ALTAR FROM THE SIXTEENTH CENTURY 213 (potash) to the batch of glass used for the house altar panels cannot be excluded. Very low iron oxide content (~ 0.1?0.15% Fe203) indicates that good quality sand was used as raw material. The presence of manganese dioxide (~ 0.5% MnO) suggests the addition of'glass makers' soap' (Mn02) as decolourizer. Recent analytical research by M?ller on medieval and post-medieval glasses [12] has shown that the glass composition found for the house altar panels is the most typical for sixteenth-century colourless (vessel) glass from South Germany. However, it could have originated elsewhere in Central Europe, for example Saxony, Bohemia or Eastern Austria. An import of the glass panels from regions producing mainly sodium-rich glass at that time, e.g. Italy and also Tyrol (Austria), can be ruled out [12, especially pp. 194-220]. Binding media The technical literature on reverse paintings on glass mentions a wide variety of possible binding agents, such as drying oils, natural resins and gums [4, pp. 39?40, 14]. Yet in-depth analyses of binding media are rare. For the identification of binding media of the house altar, five small samples (~ 0.5 mg) from the St Bridget panel were used. The binding media were first analysed by gas chromatography (GC) and gas chromatography?mass spectrometry (GC-MS). A special solvent extraction scheme for aged and altered materials was used for sample preparation [15]. With the help of various polar solvents complex mixtures of components with different polarity, such as waxes, oils and resins can be pre-separated, thus yielding more easily interpretable chromatograms. The solvent extracts were directly injected into the GC or GC-MS without prior derivatization. Instead of derivatization, oxalic acid (10% w/v) was added to the methanol extracts (see Appendix). The transparent samples of red, brownish-red and green paint were easily soluble in methanol and gave very similar GC-MS results with only slight variations in the quantitative composition. The main compo nents in these samples were diterpenoid resin acids of the abietane type (dehydroabietic acid), apart from a minor variety of oxidized and dehydrogenated diter penoid resin acids (e.g. 7-oxo-dehydroabietic acid, 7-oxo-dehydrodehydroabietic acid). Resin acids of the abietane type are the most abundant components of diterpenoid natural resins from the Pinaceae family. In particular, colophony, the resin of pine trees (Pinns), was widely used in art and craft. Due to isomerization and disproportionation reactions during the distillation process of the pine resin, abietic and particularly dehydroabietic acid are formed from a varying number of diterpene resin acids [16]. On long exposure to air and light the resulting relatively stable dehydroabietic acid will oxidize to form several oxidized products [17, 18]. In contrast to these ageing processes, the high content of oxidized and dehydrogenated resin acids in the analysed samples is only explicable by strong heating of the resin [19]. Research on resin and tar production revealed that certain types of resins can be obtained by melting at high temperatures. The resins obtained after indirect heating of the resinous wood contain isomerized and dehydrated products including dehydroabietic acid and dehydrodehydroabietic acid (abieta-tetraenoic acid) as well as oxidized products like 7-oxo-dehydroabietic acid and 7-oxo-dehydrodehydroabietic acid. The main components now present in the Corning altar samples are therefore the degradation and heating products of former pine resin (Figure 5,Table 1). In addition, neutral diterpenoid components from larch turpentine (epimanool, larixol, larixylacetate, Figure 6) could be identified [20, 21]. Balsamic larch turpentine originates from the Larix species (e.g. Larix decidua Mill.), which grow in the Austrian-Tyrolean region. Larch turpentine belongs to the group 'fine turpentine', which does not tend to crystallize and retains a long-lasting elasticity. Even today, larch turpentine (in combination with Canada balsam) plays a special role in the glass and optical industry, where it is used as high-grade glue for glass prisms and glass panels [22]. Only minor amounts of a third resin could be found in the triterpenoid region of the chromatogram (Figure 6). Small amounts of noroleanenone and other related oleanane structures were identified, which serve as useful compounds in the identification of aged mastic resin [23]. Mastic is the resin of the mastic tree (Pistacia lentiscus L.), of the Pistachio family. Its natural distribution area encloses the coastal regions of the Mediterranean Sea, but most mastic comes from the Greek island of Chios. After nearly 400 years, some volatile compounds were still detectable in the samples. Due to the thickness of the paint layers, small amounts of monoterpenoids camphor and cineole are preserved. Camphor is originally contained in the bark of the camphor tree (Cinnamomum camphora) and was added as softener [24]. 1,8-cineole (eucalyptol) is no constituent of the resins analysed but derives from the addition of an essential oil as solvent for the resin mixture. A cineole-rich essential oil (spike oil) was produced from the lavender subspecies Lavendula STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 214 S. BRET2, U. BAUMER, H. STEGE, J. VON MILLER AND D. VON KERSSENBROCK-KROSIGK Oxidation DA Dehydroabietic acid 7-Oxo-dehydroabietic acid ODA DDA ODDA Figure 5 Green lacquer layer, gas chromatogram of the methanol extract. The addition of oxalic acid leads to a slightly changed polarity of the non-polar separation column and the resin acids could be separated. The structures of the most stable pine resin compound (dehydroabietic acid) and its oxidation product (7-oxo-dehydroabietic acid) are given. Abbreviations: C = camphor, DA = dehydroabietic acid, DDA = dehydrodehydroabietic acid, ODA = 7-oxo dehydroabietic acid, ODDA = 7-oxo-dehydrodehydroabietic acid. ? Doerner Institut, Munich. Table 1 Summary of binding medium components identified with their origin and colourants of the paints (Saint Bridget panel) Components identified Origin Red sample Red-brown sample 'Green' sample 'Blue' samples (now brown) (now greyish-black) dehydroabietic acid dehydrodehydroabietic acid 7-oxo-dehydroabietic acid 7-oxo-dehydrodehydro abietic acid epimanool larixyl acetate larixol 28-nor-olean-17-en-3-one camphor 1,8-cineole (eucalyptol) amino acids (mainly serine and glutamic acid) fatty acids (mainly palmitic and stearic acid) colourants heated and oxidized pine resin larch turpentine mastic camphor spike oil aged egg protein ] (fat) cochineal, dragon's blood (+) dragon's blood copper resinate smalt, lamp black (thin, black layer) Abbreviations: +++ = main component, ++ = minor component, + = small amounts, (+) = trace amounts, - = not detected. STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions A GERMAN HOUSE ALTAR FROM THE SIXTEENTH CENTURY 215 Larjxyl acetate L2 DA ODA Figure 6 Red lacquer layer, gas chromatogram of the methanol extract. In the pure methanol extract, without further derivatization agents, the neutral diterpenoid markers for larch turpentine (L1 and L2) are clearly visible. The structure of the main component of larch turpentine, larixylacetate, is given. Abbreviations: C = camphor, L1 = epimanool, L2 = larixylacetate, DA = dehydroabietic acid, ODA = 7-oxo-dehydroabietic acid, M = noroleanenone (mastic). ? Doerner Institut, Munich. latifolia (Spike lavender) [25], Hence, spike oil was used as a solvent for this resin mixture (Table 1). Samples taken from an area that was originally blue were found to contain the pigment smalt (see below) and revealed similar resin mixtures (larch turpentine, oxidized pine resin, mastic), but also small amounts of saturated fatty acids in a ratio which is not characteristic of drying oils but rather of compounds from protein aceous media. Hence the non-soluble residues of the blue samples were further investigated by amino acid analysis [26]. The amino acid profiles of the hydrolysed samples clearly showed the presence of an aged and degraded egg binding medium. In coherence with the fatty acids detected in the solvent extracts, these markers hint toward a 'fat' egg binding medium (entire egg or egg yolk). It is possible that egg was first used to help grind the pigment, while the resin mixture served as painting medium. Colourants and metals Five colourants (Table 1) were identified in red, brownish-red, green and blue paint samples from the St Bridget panel. Scanning electron microscopy/energy dispersive X-ray microanalysis (SEM-EDX) and ^, high performance liquid chromatography (HPLC) with ultraviolet-visible (UV-VIS)-detection and GC-MS were used for the analysis. No samples of the flesh tone were available for analysis. The red lake contained carminic acid, which was identified by its retention time and UV-VIS spectrum using HPLC. Carminic acid is the main colourant of cochineal, one of the most valuable organic lakes used for paintings in the late sixteenth century [27, 28]. Due to the minute sample size, no minor components of the lake could be detected, which left no means to determine the provenance of the cochineal lake more precisely. STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 216 S. BRETZ, U. BAUMER, H. STEGE, J. VON MILLER AND D. VON KERSSENBROCK-KROSIGK Small amounts of aged dracorhodin and characteristic triterpenes from dragon's blood, a red plant resin, here of the Daemonorops draco species, were detected in red and brownish-red samples by GC-MS [28, pp. 142f., 29, 30]. This reddish-brown resinous plant exudation originates from Indonesia (Sumatra/Borneo). Although dragon's blood is frequently mentioned in historical sources, its analytical identification on sixteenth century art works has rarely succeeded so far. The bluish paint layer was found to contain smalt as the main pigment (it also contains traces of dragon's blood, presumably from an adjacent red paint). Significant amounts of arsenic and iron, and traces of bismuth, copper, nickel and zinc were detected by SEM-EDX and E They are typical for smalt of the second half of the sixteenth century, which was mostly extracted from cobalt ores in the Erzgebirge (Ore Mountains between Saxony and Bohemia) [31, 32]. Using smalt, the artist of the house altar may have tried to minimize the costs of materials. The low refractive index of smalt (1.49-1.53) is close to that of the resinous binding medium that was used, and makes it an ideal translucent colourant for this paint composition. Whereas the use of smalt in easel painting is somewhat difficult because of floating and dripping of the wet paint [33], in reverse paintings on glass the blue pigment advantageously settles down on the glass while the paint dries, and thus becomes highly visible through the glass. The greenish-brown paint layer was found to have a high content of copper. SEM-EDX analysis showed that copper is homogeneously distributed throughout the lacquer without showing distinct pigment particles. Keeping the results of the binding medium analyses in mind, this is one of the rare cases where copper resinate could unambiguously be identified in such a glaze. The colourant may have been produced in the artists' workshop by boiling a copper compound such as verdigris with the resin(s) as described in the De Mayerne manuscript (c. 1620?1646, e.g. fol. 31 and 31 [34, 35]), which explicitly mentions the use of this compound on gold and silver foil as well as on glass. However, it is also possible that the copper resinate slowly formed over the centuries as a reaction product of verdigris and the resinous medium. The green paint layer is noticeably thicker than the other lacquers, and it has an even surface with no visible brushstrokes. The silver area that represents the flesh was, as men tioned earlier, coated with a black, opaque paint, which contains a finely dispersed black pigment, presumably lamp black. Gold and silver foils were used to create the amelierung effect. Both metals were found to be of high quality with only about 5 wt% Ag in the gold and no other metal in the silver in amounts that could be detected by SEM EDX. A heavily corroded metal foil on the reverse side of one of the panels (Seven Sorrows), which protected the silver layer, was identified as pure tin foil (thickness about 7 ). 6 size used to apply the gold and silver leaf on the glass could not be identified because the coating was extremely thin. DISCOLOURATION AND DIGITAL RECONSTRUCTION Although the paint layers were protected against UVB and UVC light by the glass substrate, the binding medium was aged. It had become brittle and changed from the original light yellow to a deeper yellow or even darker tone. The latter is most obvious in the original blue paint layer (see below), whereas the optical effect of yellowing is far less evident in the red lacquer. The red paint colour is in comparably good condition, although some uneven fading has been observed in transmitted light (Figure 7). The light-fastness of the two organic colourants identified is different: cochineal on alum substrate is considered one of the reasonably stable red lakes available in the sixteenth century [36], whereas dragon's blood is usually described as being prone to fading. Artificial ageing tests of this resin has confirmed the low light-fastness but showed considerable difference in stability between the various botanical sorts and binding media [37]. The intense green areas depicting meadows (Figures 2 and 3) are greenish brown today. These areas only reveal their original green colour in transmitted light. The discolouration is most likely due to yellowing of the medium and to a greater extent to the browning of the copper glaze. This impermanence of copper resinate and also verdigris glazes is a well-known phenomenon in painting [38], yet its discolouration mechanisms and the accelerating factors are not yet entirely understood. However, the final formation of brown CuO is suggested by various authors as a possible cause for the discolouration [35, pp. 150f, 39]. Deterioration and colour change of the formerly blue areas of the sky and the background of the medallions (Figures 2 and 3) are comparably severe. Smalt has partially discoloured due to the well-known process of leaching of potassium from the pigment particles. Interestingly, the condition of the binding medium and thus its effect on the optical appearance of the blue paint STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions A GERMAN HOUSE ALTAR FROM THE SIXTEENTH CENTURY 217 Figure 7 Virgin as Queen of Heaven in transmitted light, with reintegrated paint flakes. Fading of carmine and dragons' blood can be seen. ? Simone Bretz, Munich. shows variations: in some areas the binding medium, which was identified as a mixture of resins with egg, appears extremely darkened or even black. Similar darkening is typical for oil paint layers that contain degraded smalt. Saponification products are mentioned as a possible factor [40], yet the chemical processes in the medium used here may be different. In other blue areas of the Corning altar, the paint is totally opaque, giving a milky, light-blue appearance. A cross-section revealed strong degradation of the binder in the back-scattered electron image with several micro-cavities probably acting as light-scattering sources (Figure 8). In order to have a better idea of the original appear ance of the house altar, given the severely obscured tonality of the glass paintings, a digital reconstruction of the panel Crucifixion was made. Only the original green and blue parts, which were found to be most heavily affected by colour changes, were digitally rendered. Based on the visual colour estimation of the remaining green and blue spots visible under magnification in transmitted light and on the knowledge of the original colourants through analysis, paint trials with smalt of dark quality and copper resinate, bound in a natural resin mixture (colophony, mastic in ethanol) were prepared. Using Photoshop? CS2, the blue and green areas were isolated and their colour values selectively adjusted until they visually matched the paint samples provided. Figures 2, 3 and 9 compare the condition and tonality of the central panel of the house altar before and after the conservation treatment and as a result of the digital reconstruction. CONSERVATION All seven panels with reverse painting on glass are set into an oak frame and held in place by ebony veneer. The construction is simple, but finely detailed. The original joints were made with animal glue.The glass panels were dismantled by removing the veneer frames mechanically without any use of solvents to avoid possible damage to the paint layers. The surface of the ebony veneer was cleaned with distilled water and white spirit afterwards to remove accumulated grime and dirt. In order to gain access to the decorative layers of the reverse paintings on glass of the house altar, the paper covering the reverse sides of the glass panels had to be removed, together with the silver foil. Unexpectedly, up to 30% of the paint was found to be stuck to the foil (Figure 10). The edges of some of the flakes were not sharp and thus seemed to have softened due to heat. The paint transfer was probably caused by exposure to heat when the house altar had to be dried after the flood at Corning in 1972. The most time-consuming part of the conservation work was the transfer of paint back onto the glass. Paint flakes were trapped under lifting paint and needed to be retrieved. Where possible, each flake of paint was reattached in its original position. At the beginning it seemed that the decoration had suffered extensive loss. After conservation only minor losses of not more than 1-2% were apparent (Figure 2). Since there are many different types of reverse paint ing on glass, each one requires an individual approach to its treatment. Several conservation materials have been tested within the last 20 years to identify suitable materials for the adhesion of flaking paint to a glass substrate, such as acrylic resin, polyvinyl acetate, hydrocarbon resin, ketone resin, cellulose, natural resin, animal glue and wax [9]. The requirements for the consolidating material are STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 218 S. BRETZ, U. BAUMER, H. STEGE, J. VON MILLER AND D. VON KERSSENBROCK-KROSIGK (b) Figure 8 (a) Light microscopical image of a blue cross-section, 200*. The sample was extremely brittle and difficult to polish. Residues of the polishing material in surface fractures render the sample whitish, (b) Back scattered electron image of the blue paint layer at higher magnification showing a highly degraded binding medium between the smalt particles. ? Doerner Institut, Munich. as follows: the coating has to provide excellent adhesion to the glass and should have some flexibility (adequate transition temperature, Tg). It should not have any visible impact on the artefact. The refractive index should be equal to the paint medium to minimize reflection at the interface. It must be compatible with organic materials to avoid discolouration of the original paint. The advantage of solvent-based consolidant systems for reverse paintings on glass is their ability to bond the delaminated paint in low concentrations as a pre Figure 9 Crucifixion, digitally reconstructed colour appearance. ? Andrew M. Fortune, Corning Museum of Glass, Corning (NY). liminary application. Where loose paint fragments have been dislodged and have to be reintegrated in the paint layer, resin solutions are very useful to make them adhere to the glass again. The consolidation resin used for this purpose on the house altar paintings was the hydrogenated hydrocarbon resin Regalrez 1094? in a 20% (w/v) solution in white spirit. The disadvantage of such a conservation material is that after the evaporation of the solvent a high proportion of voids become visible after a period of time. In order to eliminate this, a subsequent treatment with an adhesive-like wax was experimented with on delaminated reverse paintings on glass and proved to be successful. In the case of the house altar a sheet of silicone paper was coated with molten TeCerowax 30445 (a microcrystalline hydrocarbon wax) and placed face down on the damaged paint layer. Pressure and heat applied by a heated spatula needed to be adjusted depending on the level of damage. The STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions A GERMAN HOUSE ALTAR FROM THE SIXTEENTH CENTURY 219 Figure 10 Detail of St Dorothy: (a) reverse side during conservation; (b) large parts of the paint layer are attached to the silver foil and paper. ? Simone Bretz, Munich. softening of the original resin medium during thermal treatment enabled the closing of gaps between paint islands and the flattening of concave flakes, yielding a uniform paint layer which was not achievable by using a solvent-based consolidant alone. A brilliant saturation of the original paint was the result. A thin wax coating was left on the paint layer, which can be reactivated by reheating in case of further delamination from the glass. Finally, the conserved glass panels were set into their original positions and the ebony veneer frames were reattached with animal glue. Pieces of missing wood were replaced with new ebony veneer. CONCLUSION The technical and scientific research, conducted prior to the conservation treatment of the reverse paintings on glass of the Corning altar gave valuable insight into the still rather little-investigated amelierung technique. The colourless glass panels, which are not significantly altered, are of good quality and might well be a regional product. The binding medium is a mixture of various resins with good adhesion properties, which is important for its application to a non-porous substrate like glass. Quite unexpectedly, no drying oils or gums were found, and only blue samples contained some egg. The most abundant components derive from aged and oxidized pine resin (colophony), which had most likely been heat-treated. The processed pine resin was modified by the addition of different softeners, i.e., larch turpentine (also known under the trade name 'Venetian turpentine'), mastic and camphor. In some layers remnants of spike oil were preserved. The identified resin mixture is therefore composed of regional materials STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 220 S. BRETZ, U. BAUMER, H. STEGE, J. VON MILLER AND D. VON KERSSENBROCK-KROSIGK (pine resin, larch turpentine) and imported, exotic resins (mastic, camphor). For the colourants, this situation is much the same: the artist used costly and exotic goods (cochineal, dragon's blood, high-quality noble metals) as well as cheaper and locally available materials (smalt, copper resinate or verdigris, lamp black). The colour changes observed on the reverse paintings on glass most heavily affect the formerly blue and green parts of the composition. These are due to chemical reactions of the pigments in conjunction with degradation of the resinous medium. Fading was observed in the red organic colourants. It is hoped that future scientific research on reverse paintings on glass will allow discussion of the technical and material particularities of the Corning house altar in a broader context. The technique and state of preservation of each reverse painting on glass is unique and thus requires an individual approach for the choice of material and treatment. The speciality of the amelierung technique which only uses lacquers enabled the conservation as described. For the house altar panels the use of a single consolidant would have been preferable. However, without any pre-fixation of the loose paint particles with the resin (Regalrez 1094?,), the reintegration of the flakes back onto the glass support would not have been possible. The fragments would have been displaced by the treatment using molten wax (TeCerowax 30445) alone. Only by combining these two conservation materials could a consolidated and saturated amelierung paint layer be achieved. APPENDIX: EXPERIMENTAL DETAILS OF MATERIAL ANALYSES; MATERIALS AND SUPPLIERS Sample treatment for binding media analysis Samples were pre-treated for GC-MS by step-wise extraction with different solvents: isooctane, methanol, chloroform/methanol (7:3 v/v), oxalic acid in methanol (10% w/v) (all solvents of gas chromatogaphic grade, supplied by Merck chemicals, and anhydrous oxalic puriss by Fluka company). The solvent extracts were injected into the GC-MS without derivatization. Aged resins are unstable even in common solvents and show considerable compositional changes within a few days; therefore the extracts were analysed within a few hours. The most straightforward identification of natural resins is by non-acidic marker compounds that can be detected in the underivatized methanolic extract. Resins are also very sensitive to unsuitable preparation procedures, and drastic methylation methods, in particular those using strong acid or basic catalysts, should be avoided. Therefore, anhydrous oxalic acid (5?10% w/v) was added to the methanolic extract in an additional analysis step. In the gas chromatogram of these acidified solu tions, non-acidic diterpenes are strongly attenuated and no longer detectable, while diterpenoid acids elute with fairly good response factors and are separated well. In that step, resins with a high amount of diterpenoid acids, such as pine resin and colophony, can be identified. The approach described here does not provide a full analysis of all chemical compounds in a sample. Instead it is optimized to obtain patterns and marker compounds that enable the identification of the specific types of natural resins that are used in art [30]. Moreover, similar resins can be distinguished in mixtures, and conclusions on treatments during the manufacturing process (e.g. thermal treatments) can be drawn even from aged samples. Proteinaceous binding media were identified based on their amino acid composition. In order to release amino acids from proteins, the sample residues from the solvent extraction described above were hydrolysed with boiling HCl (6 ) for 24 hours under vacuum. If necessary, metal ions from pigments were precipitated with 8-hydroxy quinoline at pH 9 and removed by filtration with a C18 cartridge. The amino acids were collected by an acidic buffer and separated in an amino acid analyser (see below). Gas chromatography Gas chromatography was performed using an Agilent GC 6890 with autosampler equipped with a DB-5ht column (-40 to 400?C, 15 m, 0.32 mm ID, 0.1 film thickness, J & W company). Measurement conditions were the following: carrier gas helium 5.0 (purified with heated high-capacity gas purifier, Supelco company), constant-flow mode, 1.7 mL per minute; split/splitless injector: injection temperature = 250?C, splitless mode, 1 . injection volume, 0.5 minutes splitless; purge flow 36 mL per minute; oven programme: TI = 55?C, tl = 1 minute, Rl = 11?C per minute, T2 = 150?C, R2 = 10?C per minute, T3 = 360?C, t3 = 5 minutes; flame ionization detector (FID), detector temperature = 360?C. Gas chromatography-mass spectrometry GC-MS analysis was performed using a gas Chromato graph of the Hewlett-Packard (now Agilent) HP 5890 STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions A GERMAN HOUSE ALTAR FROM THE SIXTEENTH CENTURY 221 series II coupled to a Hewlett-Packard quadrupole mass spectrometer type 5989B, MS Engine, in the electron impact (El) mode, scan range 40-500 m/z.The Chromatograph was equipped with a DB-5ht column (5%-phenyl-methyl-polysiloxane), 30 m, 0.25 mm ID, 0.1 film thickness (J & W). Measurement conditions were as follows: carrier gas helium 5.0 (purified with heated high-capacity gas purifier, Supelco company), constant-flow mode, 1.7 mL per minute; split/splitless injector: injection temperature = 250?C, splitless mode, 1?2 . injection volume, 0.5 minutes splitless; purge flow 36 mL per minute; oven programme: Tl = 55?C, tl = 1 minute, Rl = 14?C per minute,T2 = 150?C,R2 = 10?C per minute, T3 = 360?C, t3 = 5 minutes; US National Institute of Standards and Technology (NIST) library, version 05. Amino acid analyses For amino acid analyses (AAA), ion exchange liquid chromatography with post-column derivatization (reagent ninhydrin, supplied by Merck chemicals) and photometric absorption detection (570 nm, 440 nm) was applied using a Biotronik LC 5001 with autosampler and a separation column with cation exchange resin (resin type BTC 2710, 210 mm length, Biotronik company). Measurement conditions were as follows: hydrolysate buffer system with sodium citrate buffers (pH 2.2-13), injection volume 50 ., flow rate 30 mL per minute. For a full description see [41]. High performance liquid chromatography The red lake was identified using a Hewlett-Packard 1050 HPLC system consisting of a 7125 injection system (20 . sample loop), gradient pump, diode array detector 1100 with microcell and HP Chemstation. UV-VIS spectra were measured between 200 and 600 nm; detection wavelength was set at 275 nm, reference wavelength at 550 nm (band with 4 and 100 nm). For separation a C18 column (column type HyperClone 5 u ODS (C18) 100 x 2.00 mm 5 micron, supplied by Phenonemex) was used. Eluents were distilled water/0.1% trifluoroacetic acid (A) and acetonitril/0.1% tetrafluoroacetic acid (B). Gradient elution A:B from 95:5 to 5:95 within 40 minutes, then kept for 5 minutes. Flow rate 0.8 mL per minute (method after Halpine [42]).The sample was dissolved in oxalic acid/methanol (10% w/v), the reference samples in methanol/HCl (1% v/v). Preparation of cross-sections Paint cross-sections were embedded in Technovit? 2000 LC (UV-hardening acrylic resin, supplied by Heraeus Kulzer) under water-jet vacuum, pre-ground with Leco Grit 400 and 1200 (Leco corporation) and polished with Micro-Mesh? cushioned abrasives (supplied by Dick GmbH) down to grade 12000. Light microscopy Light and fluorescence microscopy was carried out on an Zeiss Axioskop with filter 'DIC for direct light. Images were taken with a digital AxioCAM MRc microscope camera and AxioVision 3.1 software (Zeiss). Scanning electron microscopy/X-ray microanalysis SEM-EDX analyses were undertaken with a Philips (now FEI company) XL 20 electron microscope with an EDAX (now AMETEK) Si(Li) detector and Genesis software (EDAX / AMETEK) at the following measurement conditions: 25 kV, 30 A, 1000 cps, 100 s live-time, standardless ZAF quantification. Micro X-ray fluorescence spectrometry For energy-dispersive XRF, a portable Mikro TAX spectrometer (Bruker company) with Mo-microfocus tube (30 W), poly capillary, peltier-cooled SDD detector and helium purging was made available by the Federal Institute of Material Testing and Research, Berlin. Measurement conditions: 45 kV, 600 A, 100 s live time, semi-quantitative calibration with various standard glasses of NIST, The Corning Museum of Glass and the Federal Institute for Material Testing and Research (BAM). Materials for conservation and paint trials Smalt (No. 10000), copper resinate (No. 12200) and Regalrez 1094?: Kremer Pigmente, www.kremer-pigmente.de TeCerowax 30445:Tromm Wachs, www.wax-tromm.de ACKNOWLEDGEMENTS The authors would like to acknowledge the conservation treatment grant approved by The Getty Foundation and are very grateful for the support. The authors would like to thank Cornelia Tilenschi, Karin Lutzenberger and Irene Fiedler, Doerner Institut in Munich for carrying STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 222 S. BRETZ, U. BAUMER, H. STEGE, J. VON MILLER AND D. VON KERSSENBROCK-KROSIGK out the SEM/EDX, HPLC and amino acid analyses; Oliver Hahn, Federal Institute for Material Testing and Research (BAM) in Berlin for his support with the XRF measurements in Munich; and Andrew M. Fortune, assistant photographer and digital image special ist at The Corning Museum of Glass for the digital rendering of the house altar. Sandra Davison, private glass conservator in Thame, UK, is warmly thanked for valuable corrections and comments on the manuscript. REFERENCES 1 Ryser, F., Verzauberte Bilder. Die Kunst der Malerei hinter Glas von der Antike bis zum 18. Jahrhundert, Klinkhardt & Biermann, Munich (1991). 2 Ryser, F., Reverse Paintings on Glass:The Ryser Collection, ed. and transi. R. Eswarin, The Corning Museum of Glass, Corning (1992). 3 Ryser, F., 'Hinterglasmalerei und die Kunst des "Amelierens": Ein Begriff im Wechsel der Jahrhunderte', Restauro 1 (1994) 26-31. 4 Ryser, F., 'Die Kunst zu amelieren', in 1 Amalierte Stuck uff Glas/ Hinder Glas gemalte Historien und Gem?ld'. Hinterglaskunst von der Antike bis zur Neuzeit, ed. F. Ryser and B. Salmen, Schlo?museum Murnau (1995) 25-46. 5 Bretz, S.,'Maltechnik und Glastechnik in der Hinterglasmalerei 1600 bis 1650', in Farbige Kostbarkeiten aus Glas: Kabinettst?cke der Z?rcher Hinterglasmalerei 1600-1650, ed. H. Lanz and L. Seelig, Bayerisches Nationalmuseum M?nchen, Schweizerisches Landesmuseum Z?rich, Munich and Zurich (1999) 181-219. 6 Bretz, S., and Ryser, F.,'Kleines Handbuch der Hinterglasmalerei (Petit manuel de la peinture sous verre)', in Glanzlichter. Die Kunst der Hinterglasmalerei, Mus?e Suisse du Vitrail Romont, Museum in der Burg Zug (2000) 289-315. 7 Hahn, O., 'Untersuchungen von Farbmitteln an Hinterglas bildern des 18./ 19. Jahrhunderts', in welche zuweilen Kunstwerth haben.', Hinterglasmalerei in S?dbayern im 18. und 19. Jahrhundert, Schlo?museum, Murnau (2003) 107-110. 8 Koller,J., and Baumer, U.,'Bindemittelanalysen von Hinterglas bildern des 18. Jahrhunderts', in welche zuweilen Kunstwerth haben.', Hinterglasmalerei in S?dbayern im 18. und 19. Jahrhundert, Schlo?museum, Murnau (2003) 112-114. 9 Bretz, S.,'Information on the history, technology, deterioration and restoration of reverse paintings on glass', in Conservation and Restoration of Glass, ed. S. Davison, Butterworth-Heinemann, Oxford (2003) 341-343. 10 Volk, P., 'Hinterglasmalerei aus dem Bayerischen National museum', Kunst & Antiquit?ten 2 (1988) 52-63. 11 Pettenati, S., / vetri dorati graffiti e i vetri dipinti, Museo Civico, Turin (1978) 52-53, no. 89, plate XIII, 95-98. 12 M?ller, ., Farbloses Glas im Wandel der Zeit: Materialanalytische Untersuchungen an farblosen Gl?sern des 13. bis 17. Jahrhunderts mit Hilfe der Laser Induced Breakdown Spectrometry und der Mikro R?ntgen?uoreszenzanalyse, PhD thesis, Technische Universit?t Berlin (2006) 120-136,194-215. 13 Wedepohl, .H., Glas in Antike und Mittelalter: Geschichte eines Werkstoffes, E. Schweizerbart'sche Verlagsbuchhandlung N?gele und Obermiller, Stuttgart (2003). 14 Haff, C, 'Pigmente und Bindemittel der Hinterglasmalerei nach 1600 und deren Analysen', in Farbige Kostbarkeiten aus Glas: Kabinettst?cke der Z?rcher Hinterglasmalerei ?600-?650, ed. H. Lanz and L. Seelig, Bayerisches Nationalmuseum M?nchen, Schweizerisches Landesmuseum Z?rich, Munich and Zurich (1999) 220-242. 15 Koller, J., and Baumer, U., 'An investigation of the "Lacquer of the West": A methodical survey', in Japanese and European Lacquerware, ed. M. K?hlenthal, Arbeitsheft 96 des Bayerischen Landesamtes f?r Denkmalpflege, Lipp Verlag, Munich (1999) 339-348. 16 Sandermann, W,'Studien ?ber Harze,VII. Mitteilung: ?ber die Hitzeisomerisierung der Harzs?uren und die Zusammensetzung technischer Harze', Fette und Seifen 49 (1942) 578-585. 17 Pastorova, I., van den Berg, K.J., Boon, J.J., andVerhoeven,J.W, 'Analysis of oxidised diterpenoid acids using thermally assisted methylation with TMAH', fournal of Analytical and Applied Pyrolysis 43 (1997) 41-57. 18 Ribechini, E., Study of Amorphous Organic Residues in Archaeological Findings by Mass Spectrometric Techniques, PhD thesis, Universit? di Pisa (2005) 5, 44-45, 61-66. 19 Koller, J., Baumer, U, Kaup,Y, Schmid, M., and Weser, U, 'Effective mummification compounds used in pharaonic Egypt: Reactivity on bone alkaline Phosphatase', Zeitschrift f?r Naturforschung 58b(5) (2003) 462-480. 20 Koller, J., Baumer, U., Grosser, D., and Walch, ., 'Turpentine, larch turpentine and Venetian turpentine', in Baroque and Rococo Lacquers, ed. J. Koller and K. Walch, Arbeitsheft 81 des Bayerischen Landesamtes f?r Denkmalpflege, Lipp Verlag, Munich (1997) 359-378. 21 Scalarone, D., Lazzari, M., and Chiantore, ., 'Ageing behaviour and pyrolytic characterisation of diterpenic resins used as art materials: Colophony and Venice turpentine', Journal of Analytical and Applied Pyrolysis 64 (2002) 345-361. 22 Hever, J., 'L?rchenharzung', in Vom Ri? zum Rohharz - Das Ende einer forstlichen Nutzung in der ehemaligen DDR, Staatliches Naturhistorisches Museum, Braunschweig (1992) 80-87. 23 Koller, J., Baumer, U., Grosser, D., and Schmid, E., 'Mastic', in Baroque and Rococo Lacquers, ed. J. Koller and K. Walch, Arbeitsheft 81 des Bayerischen Landesamtes fur Denkmalpflege, Lipp Verlag, Munich (1997) 347-358. 24 K?hn, H., Erhaltung und Pflege von Kunstwerken, 3rd edn, Klinkhardt & Biermann, Munich (2001) 363-364. 25 Braun, M., Verbesserung der Arzneibuchvorschriften und ihre Angleichung and das Europ?ische Arzneibuch am Beispiel von ?therischen ?len, Dissertation Naturwissenschaftliche Fakult?t IV, Universit?t Regensburg (2002) 74-83. 26 Koller, J., Fiedler, I., and Baumer, U., 'Vermeers Maltechnik - eine Mischtechnik. Untersuchung der Bindemittel auf dem Gem?lde Bei der Kupplerin', in Johannes Vermeer - Bei der Kupplerin, ed. U. Neidhardt and M. Giebe, Michael Sandstein Verlag, Dresden (2004) 65-75. STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions A GERMAN HOUSE ALTAR FROM THE SIXTEENTH CENTURY 223 27 Schweppe H., and Roosen-Runge, H., 'Carmine - cochineal carmine and kermes carmine', in Artists' Pigments: A Handbook of Their History and Characteristics,,Vol. 1, ed. R.L. Feller, Cambridge University Press, Cambridge and Washington (1987) 255-283. 28 Eastaugh, N., Walsh, V., Chaplin, T., and Siddall, R., Pigment Compendium: A Dictionary of Historical Pigments, Elsevier Butterworth-Heinemann, Oxford (2004) 118f. and further references. 29 Baumer, U., and Koller, J., 'Drachenblut: Herkunft, Analyse und Verwendung', in abstract volume of the Jahrestagung f?r Arch?ometrie und Denkmalpflege, ed. U. Sch?ssler, R. Fuchs, Cologne, September (2001) 151-153. 30 Baumer, U., Dietemann, P., and Koller, J., 'Identification of resinous materials on 16th and 17th century reverse-glass objects by gas chromatography/mass spectrometry', International Journal of Mass Spectrometry, published online 30 October 2008, doi:10.1016/j.ijms.2008.09.010, in press. 31 Stege, H.,'Out of the blue? Considerations on the early use of smalt as blue pigment in European easel painting', Zeitschrift f?r Kunsttechnologie und Konservierung 1 (2004) 137?139. 32 Gratuze, B., Soulier, I., Blet, M., andVallauri, L.,'De l'origine du cobalt: du verre ? la c?ramique', Revue d'Arch?om?trie 20 (1996) 77-94. 33 Van Eikema Hommes, M., Changing Pictures: Discoloration in 15th?17th-Century Oil Paintings, Archetype Publications, London (2004) 20. 34 Van de Graaf, J.A., Het De Mayerne manuscript als bron voor de schildertechniek van de Barok, PhD thesis, Rijksuniversiteit Utrecht,Verweij,Mijdrecht (1958) 174 (no. 68). 35 K?hn, H., 'Verdigris and copper resinate', in Artists' Pigments: A Handbook of Their History and Characteristics,Vol. 2, ed. A. Roy, National Gallery of Art, Washington (1993) 148-158. 36 Saunders, D., and KirbyJ.,'Light induced colour changes in red and yellow lake pigments', National Gallery Technical Bulletin 15 (1994) 79-97. 37 Lewerentz K., Drachenblut: Materialkunde, quellenkundliche Studien zur maltechnischen Verwendung und Analysem?glichkeiten der verschiedenen Farbharze dieses Namens, Diploma thesis, University of Applied Science Cologne (2001) 75-83, Figure 5 in Appendix. 38 Woudhuysen-Keller R., and Woudhuysen P., 'Thoughts on the use of the green glaze called "Copper resinate" and its colour changes', in Looking Through Paintings, ed. E. Hermens, A. Ouwerkerk and . Costaras, de Prom and Archetype Publications, Baarn and London (1998) 133-146. 39 Van den Berg, K.J., Eikema Hommes M.H. v., Groen, K.M., and Berrie, . .,' copper green glazes in paintings', in Art et chimie, la couleur, ed.J. Goupy and J.-P. Mohen, CNRS Editions, Paris (2000) 18-21. 40 Spring, M., Higgitt, O, and Saunders, D, 'Investigation of pigment-medium interaction processes in oil paint containing degraded smalt', National Gallery Technical Bulletin 26 (2005) 56-70. 41 Fiedler, I., Anorganische Biochemie und Kunst: Zur Stabilit?t proteinhaltiger Matrices in Gegenwart anorganischer Pigmente, PhD thesis, Eberhard-Karls-Universit?t T?bingen (2001) 34-38. 42 Halpine, S.,'An improved dye and lake pigment analysis method for high-performance liquid chromatography and diode-array detector', Studies in Conservation 41 (1996) 76-94. AUTHORS Simone Bretz is a private conservator based near Munich, Germany. Since 1985 she has specialized in the conservation and restoration of reverse paintings on glass, and has acquired a unique knowledge of the painting technology and published on the subject. She has worked for a number of major museums and private collections in Europe and the United States and contributed her expertise to research projects both in Germany and abroad. Address: Schmiedeweg 28, 82496 Oberau, Germany. Email: info@bretz-hinterglas.com Ursula Baumer received a degree in chemistry from the Chemieschule Elhardt, Munich, Germany. She joined the Doerner Institut in 1988 and is working as a research chemist, responsible for organic analysis. She specializes in the analysis of ancient and modern binding media of paintings and works of art, archaeological resins and tars, lacquers and varnishes on furniture and altars. Address: Doerner Institut, Bayerische Staatsgem?ldesammlungen, Barer Strasse 29, 80799 Munich, Germany. Email: baumer@doernerinstitut. de Heike Stege received her diploma (1994) and PhD (1998) degree in chemistry from the Technical University of Berlin, Germany. She has a postgraduate degree (habilitation in 2005) in the field of modern analytical techniques especially suited to works of art made of glass and enamel. Since 2002 she has specialized in pigment research at the Doerner Institut, where she is currently head of the scientific department. Address: as Baumer. Email: stege@doernerinstitut. de Johannes von Miller has been working as a private conservator of furniture and wooden objects for more than 15 years. He specializes in the research of historic lacquer and the reconstruction of historic surfaces of wooden objects. Address: Dorfplatz 9, 83707 Bad Wiessee, Germany. Email:johannes@vonmiller. de Dedo von Kerssenbrock-Krosigk is head of the Glasmuseum Hentrich at the Stiftung museum kunst palast, D?sseldorf, Germany. After receiving his doctorate from Humboldt University, Berlin, Germany he worked at the Br?han-Museum in Berlin, and from 2004 to 2008 as curator of European glass at the Corning Museum of Glass in Corning, NY, USA. Address: Stiftung museum kunst palast, Ehrenhof 4-5, 40479 D?sseldorf, Germany. Email: dedo.krosigk@museum-kunst-palast.de STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions 224 S. BRETZ, U. BAUMER, H. STEGE, J. VON MILLER AND D. VON KERSSENBROCK-KROSIGK R?sum? ? Lors de la pr?paration du traitement de conservation d'un autel domestique de la fin du XVIe si?cle du sud de l'Allemagne, au Corning Glass Museum, orn? de peintures fix?es sous verre, on a men? des ?tudes techniques et analytiques sur le substrat de verre, les liants, les colorants et les ?l?ments m?talliques. Un examen au microscope a r?v?l? les particularit?s de la technique appel?e amelierung et de la fa?on dont le verre a ?t? manufactur?. Pour l'analyse des mat?riaux, la Chromatographie gazeuse coupl?e ? la spectrom?trie de masse, l'analyse des acides amin?s, la Chromatographie liquide haute performance, la micro spectrom?trie de fluorescence des rayons X et la microscopie ?lectronique ? balayage coupl?e ? la spectrom?trie des rayons X ont ?t? utilis?es. Le principal composant des liants ?tait une r?sine de pin chauff?e (colophane), modifi?e par l'ajout de diverses r?sines assouplissantes. La couche de peinture rouge contient de la cochenille et de petites quantit?s de sang de dragon. Les zones originales bleues et vertes, qui contiennent du smalt et du r?sinate de cuivre, ont subi d'importants changements de couleur. Les peintures fix?es sous verre ?taient en pi?tre ?tat. En raison de l'humidit? tr?s ?lev?e (? la suite d'une inondation au mus?e) et des m?canismes de vieillissement, la couche de peinture ?tait s?rieusement soulev?e, fractur?e en centaines de petites ?cailles et partiellement coll?e ? la feuille d'argent et au fond en papier. Les fragments de peinture ont ?t? remis en position sur le verre ? l'aide d'un fin pinceau et adh?r?s ? l'aide d'une r?sine hydrocarbure. Ce traitement a ?t? suivi de l'application d'une cire microcristalline qui a permis d'obtenir une saturation brillante des peintures fix?es sous verre. Cependant, le changement de couleur subsistait dans les zones bleues et vertes. Apr?s le traitement on a manipul? des images num?riques pour restituer la tonalit? d'origine pr?sum?e. Zusammenfassung ? Zur Vorbereitung f?r die Konservierung eines s?ddeutschen Hausaltares mit Hinterglaseinlagen aus dem sp?ten I6. Jahrhundert wurden technische und naturwissenschaftliche Untersuchungen des Glases, der Binde- und Farbmittel sowie der Metallfolien durchgef?hrt. Die mikroskopische Untersuchung zeigte die Besonderheiten der so genannten Amelierungs Technik und der Herstellung der Glastafeln auf. F?r die Materialanalysen wurden Gaschromatographie / Massenspektrometrie, Aminos?ureanalyse, Hochleistungsfi?ssigkeitschromatographie sowie Mikror?ntgenfluoreszenzspektrometrie und Ras t?relektron? nmikroskopie mit energiedispersiver R?ntgenmikroanalyse verwendet. Als Hauptbestandteil des Bindemittels wurde ein thermisch vorbehandeltes Kiefernharz (Kolophonium) nachgewiesen, das durch Zusatz verschiedener Weichmacherharze modifiziert wurde. In den roten Malschichten wurden Cochenille und geringe Reste von Drachenblut gefunden. In ehemals blauen und gr?nen Bereichen, die Smalte bzw. Kupferresinat enthalten, waren betr?chtliche Farbver?nderungen festzustellen. Die Hinterglas tafeln waren in schlechtem Erhaltungszustand: Wegen hoher Luftfeuchte (?berflutung des Museums), vermutlich nachfolgender W?rmebehandlung und Materialver?nderungen war die gesch?digte Malschicht gro?fl?chig vom Glas abgel?st, in zahlreiche lose Farbpartikel zerbrochen und klebte an den Hinterlagen aus Silberfolie und Papier. Nach dem Transfer der Malschichtfragmente in ihre originale Position auf dem Glas und Fixierung mittels eines Kohlenwasserstoffharzes und, in einem zweiten Schritt, mit einem mikrokristallinen Wachs, zeigten sich die Hinterglastafeln wieder strahlend. Allerdings blieben die Farbver?nderungen in den blauen und gr?nen Partien irreversibel. Ein Photo nach der Konservierung der Mitteltafel des Hausaltars wurde digital bearbeitet, um die angenommene urspr?ngliche Farbigkeit zu visualisieren. Resumen ? Como fase previa a los procesos de restauraci?n de un altar de devoci?n privada procedente del sur de Alemania del siglo XVI tard?o, que incluye siete pinturas bajo vidrio, se realiz? una investigaci?n t?cnica y cient?fica del substrato vitreo, de los aglutinantes, metales y colorantes. El examen microsc?pico inform? sobre la t?cnica llamada uamelierung" y la manufactura de los paneles de vidrio. Para los an?lisis de materiales se emplearon las siguientes t?cnicas: cromatograf?a de gases-espectrometr?a de masas, an?lisis de amino ?cidos, cromatograf?a l?quida de alta resoluci?n, as? como micro espectrometr?a por fluorescencia de rayos X y microscop?a electr?nica de barrido combinada a microan?lisis por energ?a dispersiva de rayos X. El principal componente del aglutinante se identific? como resina de pino precalentada (colofonia), modificada con otras resinas "plastificantes". La capa roja de pintura contiene cochinilla y peque?as cantidades de sangre de drag?n. Las ?reas que en principio deb?an haber sido azules y verdes, que se componen de esmalte y resinato de cobre, han sufrido un dr?stico cambio crom?tico. Las pinturas bajo vidrio se encontraban en un delicado estado de conservaci?n: debido a los altos niveles de humedad (inundaciones en el museo) y ala degradaci?n de los materiales, las capas pict?ricas se encontraban gravemente exfoliadas, fracturadas en cientos de peque?as escamas y parcialmente adheridas a la l?mina de plata y a la trasera de papel. Las part?culas de policrom?a desprendidas se transfirieron a sus localizaciones originales con un pincel fino y aseguradas mediante la aplicaci?n de una resina hidrocarbonada. A ello sigui? la aplicaci?n de cera micro-crisialina con la que se consigui? una buena saturaci?n de las pinturas bajo vidrio. Sin embargo se mantuvo la decoloraci?n de las ?reas azules y verdes. Una fotograf?a de despu?s del tratamiento fue manipulada digitalmente para recrear el probable cromatismo original. STUDIES IN CONSERVATION 53 (2008) PAGES 209-224 This content downloaded from 84.205.227.38 on Mon, 18 Aug 2014 08:48:57 UTC All use subject to JSTOR Terms and Conditions