Organicchemical Changes of Historic Seals as a Result of PaperRestoration

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Organic-chemical Changes of Historic Seals as a
Result of Paper-Restoration

• Erna Pilch, Leopold Puchinger

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Lacquer Seals
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Important Compounds of Shellac
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Non-Ethanolic Disinfection
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Different Degrees of Detoriation after Ethanolic
Treatment
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Damage of the seal doesnt appear in additional
peaks in the pyrogram compared to shellac
reference material
Institute of Chemical Engineering from Vienna
University of Technology
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Damaged Seal with 3 Additional Peaks
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Surface of the damaged Seal REM/EDX
1
2
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Components for the Production of Dummies

• lacs (shellac, gumlac)
• beeswax (2 contingents)
• resins (colophony, spruce resin, kauri)
• dyes (minium, cinnabar, red bolus, iron-oxidred)
• filling materials (gypsum, chalk)

aqueous and ethanolic treatment
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Pyrolysis Capillary Gas Chromatography of some
Lacquers
shellac
gumlac
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Badly changed Gum Lac after Ethanolic Treatment
untreated
shortly soaked in 70 ethanol after 1/2 hour
rinsed with water for 1,5 hours soaked in Ca(OH)2
for 10min
treated
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Gum Lac before and after Treatment
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Measurement on Different Areas
1
2
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Applying Different Treatments to Shellac
ethanolic treatment (0,2 Acticide), then rinsing
natural colour areas
ethanolic treatment (0,2 Acticide), then
rinsing
aqueous solution of 0,2 Acticide
white areas
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shellac (100g), colophony (11g), turpentine
(4g), gypsum (11g)
no filler
shellac (101g), colophony (11g) turpentine (6g),
gypsum (10g), iron oxide (3g)
shellac (100g), colophony (5g) turpentine (5g),
iron oxide (3g)
shellac (100g), turpentine (6g), gypsum (11g),
red bolus (2g)
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Shellac Dummie containing no Filler
shellac (100g), colophony (5g) turpentine (5g),
ironoxide (3g)
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No Presence of Colophony
shellac (100g), turpentine (6g), gypsum (11g),
red bolus (2g)
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Chalk instead of Gypsum
shellac (50g), colophony (4g) turpentine (1g),
chalk (4g) minium (1g)
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Using other Parameters of Pyrolysis Capillary Gas
Chromatography
after ethanolic treatment
shellac (50g), colophony (4g) turpentine (1g),
chalk (4g) minium (1g)
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Workshop-Beeswax
alkanes
waxester
beeswax
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alkenes with 31 and 32 carbon atoms
saturated monoesters with 40, 42, 44, 48, 50 and
52 carbon atoms
n-alkanes with 21, 23, 25, 27, 29, 31 carbon
atoms
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Beeswax/Shellac

• Palmitic acid
• Hexacosanoic acid
• Triacotanoic acid
• Hexacosanol
• Octacosanol
• Triacontanol
• Aliph. Hydrocarbons

• Trihydroxyhexadecanoic acid (aleuritic acid)
• Shellolic acid

soluble in ethanol
soluble in turpentine
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The
3 Peaks of the Workshop Beeswax and Shellac
Dummies have different RetentionTimes
Shellac dummie
Workshop-beeswax
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Identification of 3 Peaks in Workshop-Beeswax
TIC-Pyrogram
14,3 min
Shellac dummie
Workshop-beeswax
17,4 min
15,7 min
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Identification of a Peak in a Shellac Dummy
Shellac dummie
8,85 min
TIC-Pyrogram
Workshop-beeswax
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Franz I.
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(No Transcript)
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Seal of Imperator Leopold I., 1662 Wild
Mikroskop M 420 1,25
1,25
Farbtemperatur 3000K
5,8
12,5
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Damage Symptom Broken
transcription
picture
cup
bulge
Seal Leopold I., 1662
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restaurierung Adelsprivileg für Georg Milanovics,
1662
wax of original shows a gap at 17-20min
workshop beeswax
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adhesive, crystallizes
Przemysl, 13th century
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Seal of Przemysl
32/54
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Arpad von Györy, August 1917
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SphragisticTask
not in the inventory
not sure
restorable
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1257
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1291
throne type
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Stereomicroscopy of coloured and not coloured
Specimens
1291, green fragment, after melting at 80C
1662, natural couloured, after melting at80C
Leitz Wetzlar NLP 5x
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melting at 80C onto the microscope slide
historical probes
references
1589
beeswax
1662
1599
1589
1291
WSBW, cooked
WSBW
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1599
1599
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1599, 21. 6., parchment cord
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1599, parchment cord
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(No Transcript)
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Capillary Gaschromatograms
workshop beeswax
beeswax
1599
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Pyrolysis Capillary-Gas Chromatography
WSBW
beeswax
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Magnification of the melted probes
1599
WSBW
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Polarization Microscopy
1599
WSBW
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Polarization Microscopy
1291
beeswax
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polarization microscopy
1291
1666
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1589
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1589
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1589
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polarized light
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Fluorescence on Historical Seals
WSBW, cooked
beeswax
WSBW
1662
1599
1291
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Fluorescence Microscopy
1589