Instrumental Analysis on Select Samples from the Grand...

1 Grand Isle Private Car 1960-383 Interior Painted Panels (15-06-2884) EMW

Instrumental Analysis on Select Samples from the Grand Isle Private Car 1960-383 Interior Painted Panels (15-06-2884)

(AL6092 Analysis Job Number)

Executive Summary:

Sample Description Research Questions Analytical Technique(s)

2884 X.15 interlayer cleavage present from dining room (fiberboard panel)

Is zinc present in the layer associated with cleavage? Zinc is present surrounding areas of interlayer cleavage, but molecular analysis confirmed that lithopone is the associated pigment not zinc white What is the elemental composition of the various gilding layers? Earlier metal leaf is aluminum and later stencil decoration is copper, likely “bronze” powder paint

SEM-EDX Raman

2884 X.22 from service hallway (metal panel)

Is the metal leaf the same elemental composition in this sample from the service hallway compared to samples from other parts of the car? The metal leaf in early layers of this sample is also aluminum, matching the composition of samples from other parts of the car What is the distribution of zinc in this sample? Although this sample did not exhibit interlayer cleavage, zinc was detected in corresponding layers with sample X.15

SEM-EDX

2884 X.8 from west hallway (metal panel)

How does the metallic stencil decoration compare in elemental composition to the earlier leaf? The metallic stencil decoration is primarily copper with some zinc indicating a brass alloy. There is no evidence of an organic size layer. The earlier leaf is aluminum in composition and sits on an organic size layer. How does presence of zinc in the sample correlate with other samples? Can any correlation be made between UV fluorescence and zinc layers? Zinc maps similarly in the stratigraphy as in the other samples. The identification of zinc appears to correlate with the highest level of fluorescence under UV light (bright green-yellow). This correlation supports the use of UV fluorescence as a means for accurately characterizing the presence of zinc and distinguishing it from lead-based paints in the same binding medium.

SEM-EDX


Elemental analysis has been able to corroborate the relative timeline of the paint stratigraphy hypothesized in the examination report. Elemental analysis further confirms that samples from different areas of the car have the same paint history. About half the stratigraphy dates to post-1921 based on the presence of titanium. The paint history on the cove panels of this private car is an exemplary case study of the evolution of modern pigments in the early 20th century. Earlier layers were identified as lithopone using a combination of Scanning Electron Microscopy-Energy Dispersive X-ray spectroscopy (SEM-EDX) and Raman spectroscopy. These layers also likely date to the late 1920s based on the popularity of this pigment in the commercial sector at this time. Lead was confirmed throughout the stratigraphy and as the primary element in the earliest layers. Paint removal planned as part of the treatment of the panels needs to follow lead remediation safety protocol. The particle morphology and trace elements illustrated a distinction between the use of titanium white within the stratigraphy and helped provide a more concrete timeline in relation to known maintenance in the car. The paint used from 1963 on appears to have been heavily extended with filler content, most likely as a cost-cutting measure. Additional layers were more clearly defined, providing physical evidence of post-1963 maintenance campaigns at the Museum. The earlier gilding scheme was confirmed to be aluminum metal on both the fiberboard and metal panel samples. The restoration stenciling was not found to have any material relationship to earlier gilding. The hypothesis of zinc affecting the stability of the paint could not be completely confirmed. Therefore, environmental factors are likely the primary cause of paint failure within the car. More attention should be given to analysis of the environment and possible mitigation or intervention to maintain a more stable climate. Implications for Treatment: Emphasis should be placed on environmental causes for paint failure within the private car without a concrete link to inherent vice such as zinc oxide paint. Environmental data should be analyzed prior to treatment and new materials for repainting should be selected to withstand the current environment. Material composition provides further evidence that the current stencil decoration was not based on physical historical evidence. This is further justification for not recreating a stencil motif during the planned treatment. The varying concentrations of different trace elements like Si and Zn in the upper layers suggest subsequent retouching and maintenance after the 1963 restoration. It is possible that the overall current presentation surfaces date to post 1963, which provides further justification for repainting where the condition warrants.


Lead was found in some concentration throughout the stratigraphy and predominately in the first three layers. Therefore removal of the paint on the metal panels should not introduce fine particulate into the air. Chemical and/or heat-activated removal is recommended. Regardless proper personal protective equipment should be worn. The private car should be closed to the public during paint removal/lead remediation.

Purpose of Analysis: The main objective was positive elemental identification of zinc within the paint stratigraphy. With the resources available in-house at the Shelburne Museum only characterization had been possible thus far. The likely presence of zinc white paint has been linked to adhesion failure and interlayer cleavage in other studies of artistic works. Confirmation of zinc would suggest that some of the current condition of the panels is due to inherent vice. This identification would also further support scraping of the panels prior to repainting as cleavage would be likely to remain an issue. Specific identification of the elements within the paint stratigraphy would also be useful at further distinguishing the 1963 restoration campaign at Shelburne Museum from historic materials and technique. Elemental identification could suggest the presence of specific pigments that may be useful in further defining relative dates of historic paint campaigns. Background: Rogala et al. (2010) found that as zinc oxide oil paint ages unsaturated oleic acid remains with the paint film instead of oxidizing to azelaic acid. Unlike other paints, the zinc oxide crystal structure promotes a lamellar orientation of pigment surrounding fatty acid with a few cross links rather than an interwoven cross-linked system. This behavior results in a fast drying paint (Rogala et al. 2010, 105). Issues with zinc oxide and paint failure were known in the 1940s, but zinc paints were found to be acceptable for industry because they were stable for about three years or the relative schedule for repainting (Rogala et al. 2010, 106). Rogala et al. performed tensile tests on zinc oxide, lead carbonate, titanium white, cadmium


red, and lamp black. Zinc oxide was the only pigment in the test that had no elongation to break (Rogala et al. 2010, 106-107). In the canvas paintings examined by Rogala et al. (2010) cleavage tended to occur at the interface between zinc oxide paint and paint applied on top (98-99, 102). Rogala et al. (2010) found that when the paint completely failed and separated some of the zinc layer remained attached to the paint on top. Therefore, the cleavage appears to occur within the layer of zinc oxide itself. This inherent vice could explain some of the cleavage seen on the fiberboard panels, but it seems unlikely to be the reason behind failed adhesion with the metal substrate. Scope: Analysis was performed during one full day on-site at the Winterthur Scientific Research and Analysis Laboratory (SRAL)1 in Delaware. Three cross section samples (X.15, X.22, X.8) from the Private Car were used for additional instrumental analysis including Scanning Electron Microscopy-Energy Dispersive X-ray spectroscopy (SEM-EDX) and Raman spectroscopy. The cross sections had been cast in epoxy resin at Shelburne Museum Conservation Lab by Emily Wroczynski and were prepped for examination with the SEM by Catherine Matsen, Associate Scientist at SRAL. The SRAL job number for this object is AL6092. Additional analysis with SEM-EDX was performed on one sample (X.22) at Middlebury College as new questions arose. The analysis was performed by Senior Instrument Technician, Jody C. Smith at Middlebury College.

1 This analysis was performed for free because the project is part of Emily Wroczynski’s program of graduate study at the Winterthur/ University of Delaware Program in Art Conservation (WUDPAC). For non-affiliated clients, SRAL charges a fee per sample for analysis.


Results: Sample Analytical Techniques Elements/

Compounds Detected

Potential Pigments

X.15 SEM-EDX Pb, Zn, Ti, Ba, Ca (Fe, Al, Si)

Lead white, zinc white, lithopone, titanium dioxide, barium sulphate, iron oxide, calcium carbonate, calcium sulphate, red lead Silicon likely used as matting agent; alumino-silicate material typically found mixed with many naturally sourced mineral pigments

X.15 (isolated in layer with cleavage)

Raman

BaSO4 Barium sulphate, lithopone (zinc is not a strong Raman scatterer so it would not be detected)

X.22 SEM-EDX Pb, Ti/Ba, Ca, Zn, Fe (Al, Si)

Lead white, zinc white, lithopone, titanium dioxide, barium sulphate, iron oxide, calcium carbonate, calcium sulphate, red lead Aluminum attributed to gilded decoration; silicon likely used as matting agent; silicon in earliest layer could be sand particulate to provide tooth to the metal surface or leftover from sanding

X.8 SEM-EDX Pb, Ti/Ba, Ca, Zn (Al, Si, Cu, Fe)

Lead white, zinc white, lithopone, titanium dioxide, barium sulphate, iron oxide, calcium carbonate, calcium sulphate, red lead Copper and zinc (brass) correlate with metallic stencil decoration Aluminum attributed to gilded decoration; silicon likely used as matting agent; some alumino-silicate material may be residue from polishing


Sample X.15

Sample X.22

Sample X.8


Discussion: Identification of Zinc

X.15 is one of the samples that exhibited interlayer cleavage. Based on autofluorescence there was a strong likelihood that the paint layers surrounding this cleavage could contain zinc. The inherent brittleness of zinc oxide has been known to painters since it was first marketed. Recent studies have linked brittleness to the formation of zinc-oleate between zinc oxide and oleic acid in an oil medium. Upon drying a metal complex of zinc-oleate is formed creating a lamellar crystalline structure prone to interlayer cleavage (Maines et al. 2011; Jacobsen and Gardener 1941).

Initial mapping confirmed that zinc is the dominant element in the paint layers surrounding this cleavage. However, mapping at higher magnification showed the presence of barium. Barium and titanium have overlapping L and K-alpha lines respectively on the energy dispersive x-ray spectrum. Typically context and the “stair pattern” of L-lines for barium can clarify the identification.


EDX spectrum for sample X.15 at 167X magnification

In this case three compositions were possible: zinc oxide and titanium dioxide mixed together (not uncommon after the introduction of titanium dioxide), zinc oxide and barium mixed together (the barium would be acting like an extender or filler), or a completely different pigment called lithopone (co-precipitated zinc sulfide and barium sulfate). At higher magnification the mapping demonstrated that the two primary elements present in these layers were proportionately and homogenously integrated, suggesting a synthesized co-precipated rather than two separate paints mixed together (typically would be different particle sizes) (Eastaugh 2004, 248). Furthermore, the ratio of Zn: Ba is about 50:50. Earlier compositions of lithopone tended to be about 30% ZnS to 70% BaSO4 (Otterstedt and Brandreth 1998, 383), but a higher zinc-content lithopone was patented in 1931 (Stephens 1931).

Raman spectroscopy is able to detect compounds rather than just elements. This technique was used to confirm the presence of barium sulfate. The positive identifaction of barium sulfate and the homogenous map indicate that lithopone correlates to

the area surrounding interlayer cleavage. Zinc white was typically added to commercial lithopone, but in a small relative concentration (Hagar 1935, 100;


Standeven 2011, 38). Further analysis (such as GC-MS)2 would need to be performed to confirm that zinc-oleate also forms from lithopone in a drying oil. Material Identification and Relative Dating of the Paint History

The presence of different white pigments within the stratigraphy is consistent with their historical availability and popularity. Lead white, zinc white, and titanium white were the dominant white pigments throughout the first half of the 20th century (IARC 1989, 330; Learner et al. 2007, 119; Eastaugh 2004, 406). Often they were used in combination in order to exploit the best properties of each pigment (Eastaugh 2004, 413). The major elements within the stratigraphy support primarily white pigments, but macroscopically earlier layers are slightly tinted to yellow and pink/mauve colors. Some pink-red particles are visible in certain layers. Based on SEM-EDX, various iron-oxides (can range from yellow-orange-red-brown) are likely responsible for the majority of color in the stratigraphy. These are also very cheap mineral pigments and are common for architectural paints. The iron and lead throughout the stratigraphy could be possible tinting agents (red iron oxide, red lead).

2 See Maines et al. 2011 for methodology on using GC-MS to confirm the presence of zinc oleate.


Lead-based paints (available since antiquity) continued to be used until they were outlawed in the house painting industry in the U.S. in the 1970s. Given that the private car was built in 1899 it was expected that lead paint should be present. There is lead throughout the stratigraphy, but it is predominately in the lower two layers followed by a dominance of zinc in the subsequent layers. While zinc oxide has been found on easel paintings from the late 18th century it was not widely adopted until the first half of the 19th century. Many artists were skeptical and tended to mix a proportion of lead white with zinc white (Standeven 2011, 16, 38), which is evident in the SEM maps of the private car samples as well.3 Despite the attachment to excellent working properties and hiding power of lead white, painters were well-aware of the hazardous health effects of lead. Therefore, alternative white pigments began to supplant lead white especially as their availability, stability, and cost improved in the 20th century. By the 1930s lithopone and zinc white had almost entirely replaced lead white for interior house painting (Learner et al. 2007, 21). The transition from lead dominance to zinc dominance in the stratigraphy supports a relative dating of the first quarter of the 20th century.

3 It is also possible that the Pb in these zinc-rich layers was added as a metal drier, which was common to achieve a flat enamel look for interior paints (Standeven 2011, 37-38).


Despite lithopone being available from the late 19th century, 1928 marked the peak usage of this pigment in commercial trades prior to a rapid decline at the time of WWII (IARC 1989, 330). Titanium dioxide white is the one pigment that is anachronistic to the original manufacturing date of the private car (1899) and can help refine the dating of the stratigraphy. Titanium white was not available commercially until 1921. Like zinc white, titanium white did not immediately supplant other pigments and there were issues with stability based on the type of manufacturing process and synthesized mineral form.4 Titanium dioxide is the white pigment used throughout half of the stratigraphy present in the private car, but it is not always the dominant element in these corresponding layers. The difference in concentration of titanium and that of other trace elements actually helps further date these layers through association with different manufacturing processes. Where titanium is first present in the stratigraphy, it is the dominant element. This would suggest a non-composite or pure form (~98%) of titanium dioxide. This product was first available in the U.S. as “Titanox A” in 1926 (Laver 1997, 298-299). Titanium white was also manufactured as various “composites” meaning that titanium dioxide is precipitated onto a base compound, which simplifies manufacture and was originally thought to produce better optical properties (Laver 1997, 298). Barium sulfate was the most common base during early production in the U.S., but by the 1950s calcium sulfate bases had supplanted barium in the U.S. and calcium sulfate bases were also more common with the rutile form (Laver 1997, 305). Additional SEM-EDX with sample X.22 at Middlebury college provided a more

4 Titanium dioxide has two polymorphs: anatase form and rutile form. They are chemically the same pigment, but their crystalline structures differ. The rutile form is more stable, but it was not successfully synthesized for commercial production until 1937 (Laver 1997, 300). The rutile form can be distinguished from the anatase form using Raman spectroscopy or X-ray Diffraction (XRD). This additional analysis could provide slightly more refined dating for the stratigraphy, but nothing that would alter characterization of restoration material or the proposed treatment plan.


refined map of barium, which shows the highest concentration corresponding to the earlier titanium layers

The abundance of calcium in the upper layers of the stratigraphy is likely associated with a calcium sulfate base for titanium dioxide. Some of these layers correspond to the 1963 restoration, which is fitting with the transition in popularity to calcium bases just prior to this time. Calcium carbonate is also commonly used as an extender. Especially after 1960, extenders were heavily used with titanium white paints to offset the high cost of titanium dioxide. Unfortunately, extenders can also diminish the mechanical and chemically stability of a paint system (Learner et al. 2007, 24).


The titanium particles in these upper restoration layers also appear larger than those in the titanium-rich layers beneath. The rutile form is considered to exhibit slightly larger particle size than the anatase form (Laver 1997, 321). With this comparison, the lower titanium-rich layers are likely anatase and date between 1926-19455. It makes sense that the car would have been re-painted in

5 The anatase form was phased out in the early 1940s (Laver 1997, 305).


1939 when it was converted to a business car, which would be an appropriate marker for the beginning of the titanium-rich layers. There is documentation on the private car of “renovated, & varnish, cleaned” the interior in 1955. The first calcium rich layer could date to 1955 or to the 1963 restoration. It is unclear if the panels were also repainted in 1955. Samples taken from near the edge of the panels (including X.22) show a translucent red layer at this point in the stratigraphy. The high magnification of the SEM demonstrates a layering sequence typical of faux graining or staining on wood with alternating clear varnishes and pigmented glazes.


Given the sampling location this sequence is likely overlap of stain applied to the outer wooden molding. The presence of silicon within this pigmented glaze/stain is likely associated with the addition of silicone, included in formulas for exterior-grade stain for increased water resistance (Mitchell-Rose 2007). Silicone resins were available in the 1950s and silicone-based paint systems were developed in the 1960s (Witucki 2003). Therefore, this stain could not have been applied any earlier than 1950.

The first layer of titanium white above the wood stain could have been part of the 1955 refurbishing campaign as well, but it could also mark the 1963 restoration. This layer has a significant amount of silicon, which is likely from a silicon dioxide additive to the paint. Silicon dioxide is known generally as a matting agent to achieve flat enamel paints. Silicates were also added to paint systems as clarifying agents to help with flow and working properties (Learner et al. 2007, 24). Silicon dioxide was used as a coating over titanium dioxide pigments, available commercially in the 1930s, and more widely used with rutile pigments starting in the 1940s (Laver 1997, 302, 322). The presence of a clear organic coating on top of this layer typically marks the end of a campaign. In sample X.8 and sample X.22, subsequent layers above this varnish have the same composition (Ti, Ca, Si). This could indicate that retouching was


performed with remaining paint from the 1963 restoration. The subsequent layers in sample X.15 have slightly different trace elements and may indicate retouching that was performed at a later date. There is a discreet layer that is rich in silicon and zinc, which might suggest the use of a paint formulated specifically for metal surfaces (Witucki 2003; Garrison 2002, 253). This may have been applied as a primer when losses down to the metal substrate were first noticed.

The later varnish layer as well as the silicon-zinc layer can be useful markings for restoration/maintenance performed at the Museum, likely after 1963. Almost all of the cross section samples exhibit one or both of these layers.


Most inert paint additives like calcium carbonate do not greatly impact the presentation color. The difference in color between the current presentation surfaces on the panels is likely explained by varying degrees of yellowing of the binding media based. Muted fluorescence under UV light was noted in the upper most layers of the stratigraphy during initial cross section examination, but it could have been attributed to difference in pigment or binding media. The elemental


analysis confirms that both layers are titanium white. Therefore, the quenched fluorescence is likely due to an alkyd resin binder. Alkyd resins are also prone to significant yellowing (depending on light/UV exposure), which could explain some of the stark color contrast between restoration layers and previous paint campaigns (Ploeger and Chiantore 2013, 91). Further Characterization of 1963 restoration campaign One of the key components of the 1963 restoration is the stencil motif, which stylistically does not appear to have historical precedence. An earlier gilding scheme was discovered in cross section and elemental analysis was used to further compare this campaign with the later stencil decoration. The earlier gilding scheme is preceded by a translucent layer and a yellow paint layer. SEM-EDX did not detect any elements in this translucent layer, suggesting light organic elements typical of a varnish or sizing layer that would be applied before oil gilding. A yellow ground is also typical of surface preparation for oil gilding and the presence of iron in this layer suggests the use of yellow ochre for pigmentation. The metal leaf was identified as aluminum. Unfortunately, this material does not offer a specific terminus post-quem and it was recognized as a cheap alternative to both true gold leaf and metallic paints decoration in rail cars in 1898 (Copp 1898). Aluminum leaf, ribbon aluminum, and roll gold were heavily advertised by vendors in the Railway and Engineering Review, the Electric Railway Journal and the Street Railway Journal in the first decade of the 20th century.

The stencil decoration on sample X.8 did not resemble oil gilded metal leaf in cross-section. Elemental analysis confirmed a primary composition of copper with some zinc, indicating a brass alloy. This elemental analysis further removes the restoration scheme from any earlier design concepts within the car. The metallic stencil decoration is composed of individual particles that do not form a continuous layer, suggesting the use of metallic powders rather than a paint system with particles suspended in a binding medium. The lack of an organic size layer


underneath suggests that the brass or “bronze”6 powder was applied while the underlying paint layer was still wet. For adequate adhesion, this technique typically would employ oil or alkyd-based paint systems and not latex-based.

Preparation of Metallic Surfaces All of the samples chosen for further instrumental analysis were taken from metal substrates. Sample X.8 and X.15 were from panels in the West Hallway and Dining Room respectively, both of which have significant areas of loss and are in some of the worst condition within the car. Sample X.22 was taken from the Service Hallway where the panels are in fair condition. All of the cross section samples taken from the Service Hallway had an additional red ground beneath the preparation for the gilding.

6 The term “bronze powders” refers to metallic powders of copper alloys both brass and bronze (Bernstein 1991, 145).


This thin layer contains some lead, but was found to be predominately iron and silicon. Red iron oxide paints were suggested within the railway industry literature of the early 20th century as effective, yet economical protective coatings for metal surfaces (Master Car and Locomotive Painters’ Association 1915, 565-566).

The silicon was ambiguous at first and analysis at higher magnification within this layer was performed at Middlebury College using SEM-EDX. The silicon particles in the lower layer appear large and coarse suggesting that they are particulate such as sand (silicon dioxide) rather than a paint additive or a silicone-based clear coating like the silicon in the upper layers. The importance of sanding metal surfaces prior to painting was also emphasized in the literature (Master Car and Locomotive Painters’ Association 1915; Master Painters’ Association 1913), and this is likely residue from sandblasting or mechanical sanding.


The composition of the metal panels in the Service Hallway seems to more closely follow the standard protocol within the industry. This slight discrepancy between the panels is confusing but could be related to reconfiguring of the floorplan prior to converting into a business car in 1939.

Evaluation of UV fluorescence as a diagnostic tool While UV fluorescence is not a means of positive identification, it is an extremely useful tool for characterizing and hypothesizing composition of pigments and binding media. Initial characterizations about alkyd paints and zinc pigments based on UV fluorescence were confirmed by elemental analysis and empirical testing. Access to sophisticated analytical instrumentation is not always possible. The additional analysis in this case study has helped corroborate the effectiveness of inexpensive diagnostic tools such as ultraviolet light. A similar evaluation of the ability to identify zinc using UV fluorescence was completed by Travers Moffitt and Matsen in 2014. In this study a “bluish starry-like autofluorescence” was used to mark zinc pigments (Travers Moffitt and Matsen 2014, 41). Unfortunately, the color/tint of the autofluorescence is dependent on the exact wavelength range of the UV light source. Other sources have cited a “light green,” “bright canary yellow,” or “dull grayish green” fluorescence for zinc oxide (Stuart 2007, 77; Sward 1972, 162) and a “dark greenish yellow” fluorescence for lithopone (Sward 1972, 162). The case study of the private car has helped demonstrate that the intensity of the autofluorescence can also be used as a gauge. In this case study, the paint layers (not


including varnish) with the brightest autofluorescence aligned exactly with the SEM-EDX elemental mapping for zinc. However, these layers do not account for all of the zinc in the stratigraphy. The zinc in the later layers exhibit quenched autofluorescence. This is likely due to an alkyd resin binder. This case study demonstrates that color and general intensity of fluorescence can be misleading. Diagnosis should be based on relative intensity comparison within layers estimated to have similar binding media. This study could serve as reference material for characterizing other paint stratigraphies using the same microscope set-up in the conservation lab at Shelburne Museum.


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https://books.google.com/books?id=1ZI1AAAAMAAJ&q=coat#v=onepage&q+varnish%20color&f=false

https://books.google.com/books?id=3bElAAAAMAAJ&pg=PA565&lpg=PA565&dq=%22red+lead+priming+paints%22+railway&source=bl&ots=eASeXx1Msq&sig=B9q6a5dfQrDwcDKS4QX2FUsMk2U&hl=en&sa=X&ved=0ahUKEwi-_rPf76TLAhUBOD4KHc5vAJUQ6AEIHDAA#v=onepage&q=%22red%20lead%20priming%20paints%22%20railway&f=false





http://www.buildingconservation.com/articles/paintwoodweather/paintwoodweather.htm

http://www.buildingconservation.com/articles/paintwoodweather/paintwoodweather.htm

https://books.google.com/books?id=61pLWYqZTDcC&pg=PA383&lpg=PA383&dq=is+lithopone+yellowish&source=bl&ots=AIyxqAYQL-&sig=jxtPLitlAYzXlTPYCwxAEW8ZFGw&hl=en&sa=X&ved=0ahUKEwjTzrb3j53LAhXIVD4KHUrGD9MQ6AEIJjAD#v=onepage&q=is%20lithopone%20yellowish&f=false





Ploeger, Rebecca and Oscar Chiantore. 2013. Characterization and Stability Issues of Artists’ Alkyd Paints. In New Insights into the Cleaning of Paintings: Proceedings fromt eh Cleaning 2010 International Conference, Universidad Politecnica de Valencia and Museum Conservation Institute, ed. Marion Mecklenburg et al. Washington, DC: Smithsonian Institution. 89-95. Rogala, Dawn, Susan Lake, Christopher Maines, and Marion Mechklenburg. 2010. Condition problems related to zinc oxide underlayers: examination of selected abstract expressionist paintings from the collection of the Hirshhorn Museum and Sculpture Garden, Smithsonian Institution. Journal of the American Institute for Conservation 49: 96-113. Standeven, Harriet A. L. 2011. House Paints 1900-1960: History and Use. Los Angeles: The Getty Conservation Institute. Stephens, Thomas G. 1931. Process of Making Lithopones of High Zinc Sulfide Content. Krebs Pigment & Color Corp, assignee. Patent US1822911 A, filed 20 June 1929, and issued 15 September 1931. http://www.google.com/patents/US1822911 Stuart, Barbara. 2007. Analytical Techniques in Materials Conservation. West Sussex, UK: John Wiley & Sons Ltd. https://books.google.com/books?id=o7x8MN8ick0C&pg=PA77&lpg=PA77&dq=zinc+white+brighter+fluorescence&source=bl&ots=p8c_LE6uqw&sig=4xJ7Y6lMQL6ZGcr3o6Bsm6wREF4&hl=en&sa=X&ved=0ahUKEwiL7dGhrafLAhWLPB4KHVNeBVsQ6AEINjAF#v=onepage&q=zinc%20white%20brighter%20fluorescence&f=false Sward, G.G., ed. 1972. Paint Testing Manual: Physical and chemical examination of paints, varnishes, lacquers, and colors ASTM Special Technical Publication 500. 13th ed. Philadelphia: American Society for Testing and Materials. https://books.google.com/books?id=5SkErD0t5S4C&pg=PA162&lpg=PA162&dq=which+is+more+fluorescent+calcium+or+titanium&source=bl&ots=YPpBooZPAr&sig=LSffCVH56Cb2gCTZNZm3q86WGXE&hl=en&sa=X&ved=0ahUKEwi3lLyxq6fLAhWBGR4KHSRMDKUQ6AEISjAI#v=snippet&q=zinc&f=false Travers Moffitt, Kirsten and Catherine Matsen. 2014. Identification of zinc-based paints in cross-section using autofluorescence, SEM-EDS elemental mapping, and TSQ fluorochrome stain. In Standards in Architectural Paint Research, eds. Lisa Nilsen and Kathrin Hinrichs Degerblad. London: Archetype Publications. 41-49. Witucki, Gerald L. 2003. The Evolution of Silicon-Based Technology in Coatings. Auburn, MI: Dow Corning Corporation. http://www.dowcorning.com/content/publishedlit/26-1208-01_Evolution_of_Silicon-Based_Technology_in_Coatings.pdf

http://www.google.com/patents/US1822911

https://books.google.com/books?id=o7x8MN8ick0C&pg=PA77&lpg=PA77&dq=zinc+white+brighter+fluorescence&source=bl&ots=p8c_LE6uqw&sig=4xJ7Y6lMQL6ZGcr3o6Bsm6wREF4&hl=en&sa=X&ved=0ahUKEwiL7dGhrafLAhWLPB4KHVNeBVsQ6AEINjAF#v=onepage&q=zinc%20white%20brighter%20fluorescence&f=false




https://books.google.com/books?id=5SkErD0t5S4C&pg=PA162&lpg=PA162&dq=which+is+more+fluorescent+calcium+or+titanium&source=bl&ots=YPpBooZPAr&sig=LSffCVH56Cb2gCTZNZm3q86WGXE&hl=en&sa=X&ved=0ahUKEwi3lLyxq6fLAhWBGR4KHSRMDKUQ6AEISjAI#v=snippet&q=zinc&f=false




http://www.dowcorning.com/content/publishedlit/26-1208-01_Evolution_of_Silicon-Based_Technology_in_Coatings.pdf

http://www.dowcorning.com/content/publishedlit/26-1208-01_Evolution_of_Silicon-Based_Technology_in_Coatings.pdf


Specifications: Cross section preparation: Cross section samples were cast in epoxy Epokwick resin for mounting by Buehler using a beam capsule as a mold according to a protocol developed by Jamie Martin of Orion Analytical. A printed paper label was embedded in the resin as well. The hardened cylinder was polished using micromesh polishing clothes. SRAL SEM: The beam capsule mold allows cast cross sections to fit directly into an SEM multi-stub holder. Since the cross sections would not be cut down and put on a pin, they were wrapped in copper foil in addition to coating the polished surfaces with carbon powder (colloidal graphite in isopropanol) to make the sample more conductive and prevent charge build up. Because the sample holder from Shelburne Museum was a different height than the standard sample holder at SRAL it took some extra time to focus the SEM and find the samples. The EVO MA15 Zeiss spectrometer was operated by Associate Scientist, Catherine Matsen and an XFlash 6130 detector was used to collect data from the samples at 20kV and 1.804 Amps across a Lathanum Hexaboride filament for a minimum of 15 minutes and maximum of 1 hour per collection area. BSE images, EDX spectra, and false-color elemental maps were generated with the accompanying Esprit 1.9 software package. Middlebury SEM: The SEM-EDX analysis was performed by Jody C. Smith using a Tescan Vega 3 LMU SEM and Oxford Instruments EDS & EBSD attachments. Digital Photographic Documentation: File Name Description File Type Storage CO2015062884X8ASEMEDXspectrum Overall

spectrum of sample X8 at 161X magnification

.spx Proprietary software associated with SEM at SRAL

Cifs://sm-nas1/conservation 0Photodocumentation2884 Private Car Ceiling Instrumental Analysis X8

CO2015062884X8ABSE BSE overall 183X

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CO2015062884X8ABSE20 BSE overall 167X

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CO2015062884X8AEDXspectrum006 Spectrum of X8 at 161X converted to jpeg

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CO2015062884X8ASEMmap001 Map of Al in X8

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CO2015062884X8ASEMmap002 Map of Ca in X8

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CO2015062884X8ASEMmap003 Map of Ca, Ti, Zn, Al in X8

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CO2015062884X8ASEMmap004 Map of Cu in X8

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CO2015062884X8ASEMmap005 Map of Cu, Al in X8

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CO2015062884X8ASEMmap007 Map of Fe in X8

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CO2015062884X8ASEMmap008 Map of Pb in X8

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CO2015062884X8ASEMmap009 Map of Pb, Ca, Ti, Cu in X8

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CO2015062884X8ASEMmap010 Map of Pb, Ti, Cu, Al in X8

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CO2015062884X8ASEMmap011 Map of Pb, Ti, Cu, Si in X8

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CO2015062884X8ASEMmap012 Map of Si in X8

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CO2015062884X8ASEMmap013 Map of Ti in X8

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CO2015062884X8ASEMmap014 Map of Zn in X8

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CO2015062884X15ABSE001 BSE overall of X15 at 167X

jpeg Cifs://sm-nas1/conservation 0Photodocumentation2884 Private Car Ceiling Instrumental AnalysisX15

CO2015062884X15ABSEDetail022 BSE detail around cleavage in X15 at 354X magnification

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CO2015062884X15ABSEdetail033 BSE detail around cleavage in X15 at 748X

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CO2015062884X15ASEMEDXspectrum023

Spectrum for detail area around cleavage X15 at 354X converted to jpeg

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Spectrum for detail area around cleavage X15

.spx Proprietary software associated


at 354X with SEM at SRAL


Spectrum for detail area around cleavage X15 at 748X converted to jpeg

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Spectrum for detail area around cleavage X15 at 748X

.spx Proprietary software associated with SEM at SRAL


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jpeg


jpeg


jpeg

CO2015062884X15ASEMmap006 Map of Pb, Ca, Ti, Zn in X15

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CO2015062884X15ASEMmap007 Map of Pb, Ti, Zn, Si in X15

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jpeg


jpeg

CO2015062884X15ASEMmap010 Map of Zn in X15

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CO2015062884X15ASEMmapDetail011 Map of Al around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail012 Map of Ca around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail013 Map of Fe around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail014 Map of Pb around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail015 Map of Pb, Ca, Ti, Zn around

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cleavage 354X in X15

CO2015062884X15ASEMmapDetail016 Map of Pb, Ti around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail017 Map of Pb, Ti, Zn around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail018 Map of Si around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail019 Map of Ti around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail020 Map of Ti, Fe, Zn around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail021 Map of Zn around cleavage 354X in X15

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CO2015062884X15ASEMmapDetail025 Map of Al around cleavage 748X in X15

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CO2015062884X15ASEMmapDetail026 Map of Ba around cleavage 748X in X15

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CO2015062884X15ASEMmapDetail027 Map of Ca around cleavage 748X in X15

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CO2015062884X15ASEMmapDetail028 Map of Fe around cleavage 748X in X15

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CO2015062884X15ASEMmapDetail029 Map of Pb around cleavage 748X in X15

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CO2015062884X15ASEMmapDetail030 Map of Pb, Zn, Ba around cleavage 748X in X15

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CO2015062884X15ASEMmapDetail031 Map of Si jpeg


around cleavage 748X in X15

CO2015062884X15ASEMmapDetail032 Map of Zn around cleavage 748X in X15

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CO2015062884X22ABSE012 BSE overall of X22 at 182X magnification

jpeg Cifs://sm-nas1/conservation 0Photodocumentation2884 Private Car Ceiling Instrumental AnalysisX22 CO2015062884X22ABSEMiddlebury015 BSE overall

and details of lower layers X22 402X, 1250X, 1560X

Word document with embedded images

CO2015062884X22ASEMEDXdetailMiddlebury016

Detail maps at first layer X22 K, Al, Mg, Fe, Ca, Si, Pb



Overall maps and BSE Si, Al, Ba, Ca, Fe, C, K, Mg, O, Zn, Na, Ti, Pb



Detail maps of first 2 layers X22 Ti, Mg, Fe, Ca, Si, Pb




Proprietary software associated with SEM at SRAL


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jpeg


jpeg


jpeg

CO2015062884X22ASEMmap005 Map of Pb, Ca, Al in X22

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CO2015062884X22ASEMmap006 Map of Pb, jpeg


Ca, Fe, Zn, Al in X22

CO2015062884X22ASEMmap007 Map of Pb, Ca, Zn, Al, Si in X22

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CO2015062884X22ASEMmap008 Map of Pb, Ca, Zn, Al, Ti in X22

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CO2015062884X22ASEMmap Map of Zn in X22

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Instrumental Analysis on Select Samples from the Grand...

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