November 17, 2010 Mr. Jeffrey Fuller Fuller Fine Art Auctions 730 Carpenter Lane Philadelphia, PA 19119 Dear Mr. Lawrence: This report summarizes the analysis of two paintings by victor Manuel. You asked that the paintings be analyzed to determine if the pigments and paint are appropriate for the proposed creation dates of the 1940s. Based on the data from the analyses performed, all of the materials in the original paintings are consistent with materials in common use in 1940s and there is significant similarity between the two paintings in regard to the paint palette used. Regarding the possibility that these may have been painted in the last five to ten years as copies of Victor Manuel paintings, based on the examination of the paintings I would say that both paintings are consistent with ages of about 60 to 70 years old. This opinion is based on the craquelure of the paintings, the state of the canvases, and the variations in the white pigments. When someone tries to fake craquelure in a painting there are methods such as heating, straining or even drawing in the cracks. The craquelure was varied over the paintings which is consistent with the different rates of aging of the different colors of paint. Also white paint with titanium dioxide pigments don t show craquelure as quickly as when lead white paint is used which also speaks to the age of the paintings. If someone had determined that a titanium white paint had been used and wanted to recreate it, currently the majority of available paints would have only the rutile phase. The transition from one form to the other in the paintings and minor components are consistent with the development of titanium white paints in the 1930-1945 period. The canvases also show what could be called a patina from aging which you wouldn t see on a more recent canvas.
Page Two Painting Description and Examination Photographs of the paintings are included in Figures 1 through 8. The paintings were analyzed sequentially so that if the materials in the first painting had been inappropriate no further work would have been done. The first painting In the Park Lot 23 is 18 ½ x 27 ½ inches and is in very good condition. The painting was examined with raking light, direct light and UV light. The paint layer was reasonably flexible and showed craquelure in some of the areas of paint. Some restoration had been performed on the painting and these areas observed with UV light were avoided for paint sample. Samples of pigments were collected using a sharpened tungsten needle. The second painting Untitled, Portrait Lot 39 is 23 x 21 inches and was examined in the same manner as the first painting. There was a greater degree of craquelure to the paint layer on this painting due to apparent aging and that the painting was likely rolled up. The canvas is also in a more degraded state relative to the first painting. This difference would be attributed to factors such as the age, storage conditions, and environmental exposure. Analysis The collected pigment and paint samples were analyzed using optical microscopy, FTIR microscopy and Raman microscopy as necessary. The use of multiple techniques provides different information about each sample. Optical microscopy provides information about pigment particle size, optical properties, homogeneity, and color. For the optical microscopy, the samples were each prepared for analysis by transferring a portion of the sample to a glass microscope slide. The sample was then covered with a coverslip and immersion oil (refractive index of 1.662) and examined with the microscope. Fourier Transform Infrared (FTIR) microscopy provides information about the molecules present including the paint medium, organic pigments, and some inorganic pigments. For the FTIR analysis a fresh portion of each paint sample was transferred to a gold slide, which is suitable for reflecting the infrared light. A spectrum of each sample was collected to aid in identification of the paint medium and pigments. Spectra from the FTIR analysis and reference spectra are included in Appendix I. Raman microscopy compliments FTIR microscopy and provides key information for some samples such as the crystal form of some oxides (e.g. titanium dioxide, iron oxides). And it can be performed on areas as small as 1 micrometer which is often the same size as very finely ground pigments. The samples prepared for FTIR microscopy were used for this analysis as well. A Raman spectrum from each sample was
collected with the Raman microscope system. All of the samples did not give useful Raman spectra, but key spectra from the Raman analysis are included in Appendix II. In the Park Painting Results Sample 1 Paint from Signature (position 2 inches from left edge and 1 inches from bottom edge) Examination of the signature showed that it was applied to dry paint. The optical microscopy analysis of the white ground layer showed birefringent reddish particles 1-5 um in diameter that were consistent with iron oxide pigment. The Raman spectrum shows bands consistent with barium sulfate, iron oxide red, and an azo yellow pigment. The FTIR spectrum of the sample showed an oil paint and a hydrated iron oxide pigment. Sample 2 Red and White (Ground) (position 2 inches from left edge and 4 inch from the bottom edge) The optical microscopy analysis of the red layer showed reddish particles consistent with iron oxide pigment particles and white particles that would be present as a filler in the paint. The optical microscopy of the white ground layer showed
Page Three magnesium carbonate (dolomite) particles and a clay. The FTIR spectrum of the red layer shows an oil paint, a carbonate component and the hydrated red iron oxide. The white ground layer is also an oil paint but has a mixture of clay and dolomite. The Raman also confirmed that the white pigment particles in the ground are magnesium carbonate. For the red paint there was a mixture of red iron oxide and an azo yellow pigment. Sample 3 White (position 10 inches from left edge and 11 inches from bottom edge) The optical microscopy analysis showed white particles <1 to 2 micrometers in diameter distributed through the paint film consistent with titanium dioxide. FTIR spectra showed that the paint medium was an oil paint but also appeared to have a protein component so there may be a glaze over the white paint. The Raman spectrum confirmed that there is titanium dioxide in a rutile form present. Sample 4 Blue (position 5 inches from left edge and 9 ½ inches from bottom edge) The optical microscopy analysis showed that the paint was a mixture of blue and a white pigments. The blue is consistent with ultramarine blue and the white is consistent with an calcium carbonate. The FTIR analysis showed that the paint medium is an oil paint with calcium carbonate filler and ultramarine. The Raman spectrum confirmed a ultramarine and calcium carbonate. Sample 5 Yellow (position 4 inches from left edge and 4 inches from bottom edge) The optical microscopy analysis showed yellow particles less than 3 micrometers in diameter and white particles less than 15 micrometers in diameter. The FTIR spectrum shows that the paint is consistent with an oil paint and calcium carbonate. Raman identified rutile titanium dioxide and an azo yellow pigment. Sample 6 Green (position 3 inches from left edge and 10 inches from bottom edge) The optical microscopy analysis showed the green color is due to a mixture of blue and yellow pigments. The blue particles were consistent with ultramarine optically. White particles with a diameter ranging from 2 to 12 micrometers were consistent with calcium carbonate. The FTIR spectrum showed a small carbonate filler and the ultramarine in an oil paint. Raman analysis showed the azo yellow pigment and ultramarine blue. Sample 7 Brown (position 2 inches from left edge and 12 inches from bottom edge) The optical microscopy analysis showed reddish brown particles between 1 and 7 micrometers in diameter consistent with iron oxide. The FTIR spectrum showed an oil paint with iron oxide. Raman microscopy identified an azo yellow pigment.
Page Four Untitled, Portrait Painting Results Sample 1 White (position 5 inches from left edge and 5 inches from bottom edge) The optical microscopy analysis of the white paint showed birefringent white particles less than 1 um in diameter that were consistent with titanium dioxide and barium sulfate. The Raman spectrum shows bands consistent with anatase titanium dioxide and barium sulfate. The FTIR spectrum of the sample showed an oil paint with barium sulfate and titanium dioxide. Sample 2 Signature (position 2 inches from left edge and ½ inch from the bottom edge) Examination of the signature showed that it was applied to dry paint. The optical microscopy analysis of the reddish orange paint showed red particles consistent with iron oxide pigment particles. The FTIR spectrum of the red layer shows an oil paint, a carbonate component and the hydrated red iron oxide. The Raman showed that there was a mixture of red iron oxide and an azo yellow pigment. Sample 3 White Ground (position ¼ inches from left edge and 2 inches from bottom edge) The optical microscopy analysis showed white particles 1 to 12 micrometers in diameter distributed through the paint film consistent with calcium carbonate. FTIR spectra showed that the paint medium was an oil paint white calcium carbonate. Sample 4 Yellow and White Ground (position 7 inches from left edge and 5 inches from bottom edge) The optical microscopy analysis showed that the paint was a mixture of yellow and white pigment. The white is consistent with an titanium dioxide. The FTIR analysis showed that the paint medium is an oil paint. The Raman spectrum showed an azo yellow pigment and anatase titanium dioxide. Sample 5 Red (position 15 inches from left edge and 1 inches from bottom edge) The optical microscopy analysis showed red particles less than 10 micrometers in diameter and white particles less than 15 micrometers in diameter. The FTIR spectrum shows that the paint is consistent with an oil paint with iron oxide and calcium carbonate. Raman identified an azo yellow pigment. Sample 6 Violet (position 1 ½ inches from left edge and 19 inches from bottom edge) The optical microscopy analysis showed the blue pigment particles consistent with ultramarine and white particles consistent with calcium carbonate and titanium dioxide. The violet color could not be seen as discrete particles. The FTIR spectrum showed an oil paint and both calcium carbonate and titanium dioxide. Raman analysis showed anatase titanium dioxide. The Raman data also gave and indication that the violet color was an azo compound.
Sample 7 Black (position 2 inches from left edge and 20 inches from bottom edge) The optical microscopy analysis showed black particles less than 3 micrometers in diameter and agglomerations of particles up to 30 micrometers. The FTIR spectrum showed an oil paint with bone black pigment and calcium carbonate. Summary The pigments and media clearly identified are consistent with those available and in use during the late 1930s to mid 1940s. Oil paint medium has been used for centuries. The pigments that were observed included three types of white pigment titanium dioxide, calcium carbonate and barium sulfate. The production of the rutile form of titanium dioxide was being refined in the late 1930s. Calcium carbonate has been used as a filler and pigment for hundreds of years. Barium sulfate was introduced in the 19 th century as a filler in paints because it does not have strong enough hiding power to be used as a white pigment by itself. The sulfate presence may also be related to the early rutile titanium dioxide form since barium sulfate was also used as a co-precipitate with titanium dioxide as the process of producing this pigment was progressing. Iron oxide pigments were originally earth based pigments used since ancient times. The red iron oxide in this painting is synthetic since it has a consistent color and particle size without associated materials of other iron oxide colors (red to black). Azo pigments had become popular in the early 20 th century and a significant amount developing variations that gave different colors. There are clear similarities between the paintings. First is that both of the paintings were done as oil paintings. Second, the colors used in the two paintings are similar. The reds and yellows that are used in the two paintings are variations of iron oxide pigments and azo pigments, and blends of these two types of pigment. From a historical point of view, these two paintings capture a period in time where there was a migration from one form of titanium dioxide (anatase) to a better performing second form (rutile). Although the paintings did not have exact dates associated with them, the older appearance of the canvas on the Untitled Portrait painting coincides with the older form of titanium dioxide. Regarding the possibility that these may have been painted in the last five to ten years as copies of Victor Manuel paintings, based on the examination of the paintings I would say that both paintings are consistent with ages of about 60 to 70 years old. This opinion is based on the craquelure of the paintings, the state of the canvases, and the variations in the white pigments. When someone tries to fake craquelure in a painting there are methods such as heating, straining or even drawing in the cracks. The craquelure was varied over the paintings which is consistent with the different rates of aging of the different colors of paint. Also white paint with titanium dioxide pigments don t show craquelure as quickly as when lead white paint is used which also speaks to
the age of the paintings. If someone had determined that a titanium white paint had been used and wanted to recreate it, currently the majority of available paints would have only the rutile phase. The transition from one form to the other in the paintings and minor components are consistent with the development of titanium white paints in the 1930-1945 period. The canvases also show what could be called a patina from aging which you wouldn t see on a more recent canvas. Thank you for consulting the Center for Art Materials Analysis, Inc. Sincerely, Kenneth J. Smith Ph.D. Reference: Project 2010-10-29-1/2
Figure 1. Photograph of In the Park painting.
Figure 2. Photograph of In the Park painting with color standards chart.
Figure 3. Reverse of In the Park painting.
Figure 4. Photograph of signature on In the Park painting.
Figure 5. Photograph of Untitled, Portrait painting.
Figure 6. Photograph of Untitled, Portrait painting with color chart.
Figure 7. Photograph of reverse of Untitled, Portrait painting.
Figure 8. Photograph of signature on Untitled, Portrait painting.
APPENDIX I FTIR SPECTRA Center for Art Materials Analysis, Inc. Project 2010-10-29-1/2
2010-10-29-1 Sample 1 - signature 0.46 0.44 0.42 0.40 0.38 0.36 0.34 0.32 0.30 Log(1/R) 0.28 0.26 0.24 0.22 0.20 0.18 0.16 0.14 0.12 0.10 0.08 0.06 2010-10-29-1 Sample 2 reddish orange 0.50 0.45 Log 0.40 0.35 1.3 2010-10-29-1 Sample 2 - white 1.2 1.1 Log 1.0 0.9 0.8 0.7
0.50 2010-10-29-1 Sample 3 white (2) 0.48 0.46 0.44 0.42 0.40 0.38 0.36 Log(1/R) 0.34 0.32 0.30 0.28 0.26 0.24 0.22 0.20 0.18 0.16 2010-10-29-1 Sample 4 blue 1.0 0.8 Log 0.6 0.4 0.2 0.0 1.3 2010-10-29-1 Sample 4 blue (associated white particles) 1.2 1.1 Log 1.0 0.9 0.8 0.7
0.95 2010-10-29-1 Sample 5 yellow 0.90 0.85 0.80 0.75 0.70 0.65 Log(1/R) 0.60 0.55 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.68 2010-10-29-1 Sample 6 green 0.66 0.64 0.62 0.60 0.58 Log(1/R) 0.56 0.54 0.52 0.50 0.48 0.46 0.44
2010-10-29-1 Sample 7 bown 1.40 1.35 1.30 1.25 Log(1/R) 1.20 1.15 1.10 1.05 1.00 0.95 0.52 2010-10-29-2 Sample 1 white 0.50 0.48 0.46 0.44 0.42 0.40 0.38 Log(1/R) 0.36 0.34 0.32 0.30 0.28 0.26 0.24 0.22 0.20 0.18
0.64 2010-10-29-2 Sample 2 signature 0.62 0.60 0.58 0.56 Log(1/R) 0.54 0.52 0.50 0.48 0.46 0.44 0.42 0.40 0.95 2010-10-29-2 Sample 3 ground 0.90 0.85 0.80 0.75 0.70 0.65 Log(1/R) 0.60 0.55 0.50 0.45 0.40 0.35 0.30 0.25 0.20
0.51 2010-10-29-2 Sample 4 yellow 0.50 0.49 0.48 0.47 0.46 0.45 0.44 Log(1/R) 0.43 0.42 0.41 0.40 0.39 0.38 0.37 0.36 0.35 0.34 0.33 2010-10-29-2 Sample 5 red 0.84 0.82 0.80 0.78 0.76 0.74 Log(1/R) 0.72 0.70 0.68 0.66 0.64 0.62 0.60 0.58 0.56
1.14 2010-10-29-2 Sample 6 violet 1.12 1.10 1.08 1.06 1.04 1.02 Log(1/R) 1.00 0.98 0.96 0.94 0.92 0.90 0.88 0.86 0.84 0.82 2010-10-29-2 Sample 7 black 0.32 0.31 0.30 0.29 0.28 Log(1/R) 0.27 0.26 0.25 0.24 0.23 0.22
1.0 CALCITE (colorless) 0.9 0.8 0.7 0.6 Absorbance 0.5 0.4 0.3 0.2 0.1
Bone black 0.9 0.8 0.7 0.6 Absorbance 0.5 0.4 0.3 0.2 0.1 0.0 1.0 Drying OIl 0.9 0.8 0.7 0.6 Absorbance 0.5 0.4 0.3 0.2 0.1-0.0
1.0 Ultramarine blue 0.9 0.8 0.7 0.6 Absorbance 0.5 0.4 0.3 0.2 0.1-0.0 2.0 PY083 diarylide yellow 1.8 1.6 1.4 1.2 Absorbance 1.0 0.8 0.6 0.4 0.2 0.0
1.0 Titanium Dioxide 0.9 0.8 0.7 0.6 Absorbance 0.5 0.4 0.3 0.2 0.1 1.0 Dolomite 0.9 0.8 0.7 0.6 Absorbance 0.5 0.4 0.3 0.2 0.1
APPENDIX II RAMAN SPECTRA Center for Art Materials Analysis, Inc. Project 2010-10-29-1/2
100 2010-10-29-1 Sample 1 signature (2) 90 80 70 60 50 40 30 20 10 0-10 4000 Raman shift (cm-1) 2010-10-29-1 Sample 2 reddish orange 360 340 320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0 4000 Raman shift (cm-1)
550 2010-10-29-1 Sample 3 white 450 400 350 300 250 200 150 100 50-0 Raman shift (cm-1) 2010-10-29-1 Sample 4 blue 1600 1400 1300 1200 1100 900 800 700 600 400 300 200 100-0 Raman shift (cm-1)
65 2010-10-29-1 Sample 4 white 60 55 50 45 40 35 30 25 20 15 10 5 0-5 Raman shift (cm-1) 550 2010-10-29-1 Sample 5 yellow 450 400 350 300 250 200 150 100 50 0 Raman shift (cm-1)
1800 2010-10-29-1 Sample 6 green (blue component) 1700 1600 1400 1300 1200 1100 900 800 700 600 400 300 200 100-0 4000 Raman shift (cm-1) 140 2010-10-29-1 Sample 7 brown 130 120 110 100 90 80 70 60 50 40 30 20 10 0 Raman shift (cm-1)
9000 2010-10-29-2 Sample 1 white 8 8000 7 7000 6 6000 5 0 4 4000-0 Raman shift (cm-1) 180 2010-10-29-2 Sample 2 signature 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 Raman shift (cm-1)
1.0 Ultramarine 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 1400 1200 800 Raman shift (cm-1) 600 400 200 titanium oxide rutile 3200 2800 2600 2400 2200 Absorbance 1800 1600 1400 1200 800 600 400 200 Arbitrary units
1.0 Calcite 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 Raman shift (cm-1) Goethite (Red Iron Oxide) 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 1800 1600 1400 1200 Raman shift (cm-1) 800 600 400 200
800 2010-10-29-2 Sample 4 yellow 750 700 650 600 550 450 400 350 300 250 200 150 100 50-0 Raman shift (cm-1) 2010-10-29-2 Sample 5 red 900 800 700 600 400 300 200 100-0 Raman shift (cm-1)
2010-10-29-2 Sample 6 violet 2800 2600 2400 2200 1800 1600 1400 1200 800 600 400 200 0-200 Raman shift (cm-1) 2010-10-29-2 Sample 2 signature 160 140 120 100 80 60 40 20 0 100 2010-10-29-1 Sample 1 signature (2) 80 60 40 20 0 Raman shift (cm-1)
2010-10-29-2 Sample 5 red -0 *2010-10-29-2 Sample 1 white-red 200 0 *2010-10-29-1 Sample 2 reddish orange 300 200 100 0 2010-10-29-1 Sample 7 brown 100 50-0 Raman shift (cm-1)