using xrd and ir-atr to determine pigment composition of ... · use x-ray diffraction (xrd) and...
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Using XRD and IR-ATR to Determine Pigment Composition of the US
5-cent 1847 Issue
Gordon Eubanks
Harry Brittain FRSC
2015 IAP International Symposium on Analytical Methods in Philately
Itasca IL 18-19 November 2015
Rev 0.10
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The Stamp
• Issued 1 July 1847
• Five distributions (printings)
• Well over 100 shades recorded– 27 major shades from brown to orange
• Original visual study of color– by Carol Chase, Calvet Hahn, Roy
White and othersBoth stamps
unused orig gum
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Previous Research
• Visual classification by Carol Chase– Studied different shades on existing stamps
– A few dozen identified
– Others (Hahn) expanded and improved
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Previous Research Part 2
• Visual classification by Carol Chase– Studied different shades on existing stamps
– A few dozen identified
– Others (Hahn) expanded and improved
• Wade Saadi Chronicle article August 2013– Used X-ray fluorescence (XRF) to study elements in ink
– Determined components in the ink are lead based
– Thus approach used can not determine which compounds of lead are present
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Color Wheel
Stamps appear to vary in color from almost
orange to dark brown.
Same stamps used by Saadi in his research
with same ID numbers.
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Average Reflectivity Per Shade
Analysis of reflected light to determine color and
luminescence of a sample. All samples from the color wheel.
Produced by Tom Lera at the National Postal Museum. Figure 4
in Saadi’s Chronicle Article.
Brown oranges and red oranges show greater luminosity.
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The Goal of this Research
Use X-ray diffraction (XRD) and infrared absorption spectroscopy with attenuated
total reflectance sampling (IR-ATR) determine the components of the ink
using the same stamps as Saadi.
In other words, Saadi determined only lead was present. What are the
components of lead?
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Infrared Absorption Spectroscopy (IR-ATR)
Average of 15 stamps in color wheel
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This is what is in the ink now
Cellulose from paper stamps printed on
Rosin binds cellulose particles in the paper
Soap is present
Reaction with lead oxide results in lead soap
Calcium carbonate is a white pigment that lightens the black and extends the ink
Infrared Absorption Spectroscopy (IR-ATR)
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X-ray diffraction (XRD)
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X-ray diffraction (XRD)
Again this is what is present now
Cellulose from paper stamps printed on
Crystalline Lead sulfide (PbS) found on stamps
Lead sesquioxide red pigment
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Compare 2 Stamps. XRD Positions L2 & R1
403530252015105
4
6
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10
12
14
16
18
20
22
Orange stamp Brown Black stamp403530252015105
4
5
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Compare 2 Stamps. IR-ATR Positions L2 & R1
Orange stamp Brown Black stamp
4000350030002500200015001000
16
24
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48
56
64
72
80
88
96
4000350030002500200015001000
16
24
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48
56
64
72
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96
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Issue That Can Affect Color
• Soap is a product of a reaction with red lead and linseed oil.
• Compounds for ink measured in different ratios
• Calcium carbonate reacts with acid in air, paper
• Reds turn orange exposed to moisture and CO2
– Van Gough’s reds
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Issues Affecting Color Not Measured
• Particle size in ink
• Soaking in water with vinegar transforms lead
• Most important what were the original components of the ink!
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So What Is the Ink Made Of?
• Eye perception of color is a poor indicator of original ink compounds
• Primary components identified• Calcium carbonate (CaCO3) – white
Finely ground chalk or oyster shells
• lead sulfide (PbS)– dark gray to black• lead sesquioxide (Pb3O4) – red lead
Known as minimum
• No Chromium compounds found
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Questions?