Escolar Documentos
Profissional Documentos
Cultura Documentos
Measurement
journal homepage: www.elsevier.com/locate/measurement
a r t i c l e
i n f o
Article history:
Received 14 June 2010
Received in revised form 10 May 2011
Accepted 21 June 2011
Available online 29 June 2011
Keywords:
Paper
Leather
Microscopes
XRD
EDAX
Microorganisms
Chemical analysis
HPLC
a b s t r a c t
The manuscript studied here dates to 19th century, and consists of paper pages and leather
bookbinding. This study aims to use analytical techniques in order to identify the components of the manuscript and to explain its deterioration process. Visual assessment, isolation and identication of fungi, pH measurements, and investigation of the surface
morphology by a scanning electron microscope (SEM) were used to explain paper and
leather deterioration. X-ray diffraction with EDAX, Fourier Transform Infrared Spectroscopy (FTIR), and chemical analysis were used to identify pigments, binder of pigments,
ash, lignin, and the a-cellulose content of papers. The shrinkage temperature measurement
was used to explain the deterioration process of leather. SEM was used to identify the type
of animal skin used for the bookbinding and high performance liquid chromatography
(HPLC) was used to identify the vegetable tanning material used with the bookbinding.
The results revealed that the ink used was a mixture of carbon with iron gall. The pigments used on the paper were gold leaf or gold shell, cobalt oxide, and mercuric sulde
for the gold, blue and red colors respectively. Sodium chloride was the main salt crystallized on the surface of paper. Calcium carbonate was the ller used in the paper making
process. Cotton bers may have been used as a raw material in the creation of paper.
The values of the shrinkage temperature and pH were lower than in normal conditions,
indicating that the leather bookbinding suffers from deterioration. Aspergillus sp., and
Penicillium sp. were the most dominant fungi found on the manuscript. Goat skin was
identied as the animal skin of the bookbinding, and Acacia Arabica was identied the
tanning material used with the bookbinding. The condition of the manuscript studied with
its components play an important role in its deterioration.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
A major problem in the preservation of cultural heritage
is the damage to manuscripts, mainly paper and bookbinding. Damage can be caused by the effect of aggressive
atmospheres, humidity and temperature, alterations of
paper constituents, and added materials such as ink and
hand coloring with pigments or dyes [1]. Deterioration of
paper-based materials is mainly due to the degradation
of cellulose caused by a number of factors, such as chemi-
2. Historical background
The manuscript was found in the library of Ahmed AlBajam Mosque, located in Mehalit Marhoum Village, Tanta
City, Egypt. It was discovered during the destruction of the
mosque. It dates back to 19th century, and contains part of
the 28th chapter of the Holy Quran. It suffers from ground
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from the corium part of the leather was wet with distilled
water for at least 10 min on a microscope slide. Then the
samples were transferred to another slide with acetone
for at least 30 min and again transferred to distilled water
and glycerin. The bers are separated, air bubbles were
removed with a needle, and the bers were well dispersed
on the slide and secured. The microscope slide was placed
on the hot table. The gradient heat controller was calibrated at 22 C, as well as 80 C to achieve the traceability
to ITS 90 (International Temperature Scale). The timer was
calibrated using a calibrated stope watch traceable to
NISTUSA (National Institute for Standard and Technology). The measurement of hydrothermal stability was
performed at the Analysis Laboratory, Animal Physiology
Department, Jagiellonian University, Poland.
3.8. Identication of animal skin used for the bookbinding
The surface examination by a scanning electron microscope, JEOL-JSM-5400LV, was used to identify the type of
animal skin used for the leather bookbinding. A specimen
of about 2 mm 4 mm was aligned on a stub, with the hair
follicles opening towards the stub as viewed under the
microscope. The specimen was mounted on stub and
coated with ne gold. The nominal thickness of the sample
was 20 nm. The study of Haines [32] was taken as a reference in order to be compared with the identied skin from
the bookbinding studied. SEM was performed at the Scanning Electron Microscope Laboratory, The central Laboratory unit, Assiut University, Egypt.
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Ash %
Lignin %
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% a-cellulose
B
100
A
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Fig. 1. Aspects of deterioration found on Quran manuscript: (1A and 1C) aspects of deterioration of a bookbinding, (1B and 1D) aspects of deterioration of
papers.
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Fig. 2. Investigation of deteriorated of paper by SEM: (A) original paper manuscript; (B) original paper with some stains and dusts; (C) original paper with
damaged caused by insects; (D) restoration paper; (E) exterior lining paper; (F) interior lining paper.
the surface of leather. Calcium was found in the high percentage of 27.77%. Magnesium, aluminum potassium, and
silicon were also found, and this may indicate that the
ground consisted of lime with traces of clay minerals and
sand. Sulfur may act as a contaminant from the surrounding environment or from the manufacturing process of
leather bookbinding. Sodium also was found and may have
derived from the burial environment of the manuscript.
The sodium was further identied as sodium chloride
and it was found on all of the paper pages of the manuscript. This type of salt led to the erosion of the surface
of both the papers and leather. The source of sodium chloride in the case study may be from saline in the soil and
groundwater, air pollution, and human contaminants. Salt
damage takes place when evaporation takes place, leaving
the salt to grow as crystals within the pores of the leather
or paper. The growth pressure of developing crystals is
very high and sufcient to cause erosion on the leather
Fig. 3. Investigation of the surface morphology of leather bookbinding by SEM and analysis of stain found on the leather surface by EDAX.
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Fig. 4. X-ray diffraction pattern of ink and pigments used on the paper of the manuscript.
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Table 1
EDAX analysis of ink and colorants used on paper manuscript.
Color
Gold
Blue
Red
Black
Elements (wt%)
Total
Na
Mg
Al
Si
Cl
Ca
Ti
Fe
Cu
Zn
Hg
Au
Co
1.37
9.20
0.80
2.65
0.22
3.03
2.45
0.43
9.79
3.65
3.24
0.58
18.93
10.67
11.32
4.15
0.71
1.19
0.27
4.43
6.02
4.59
0.15
1.54
3.15
9.35
0.60
2.12
2.05
4.09
0.88
7.66
19.37
18.40
0.33
0.28
0.78
0.73
3.82
1.32
0.78
0.82
1.24
0.30
0.62
28.50
71.17
17.33
42.63
20.95
37.12
2.22
Fig. 5. FTIR analysis of gum Arabic binder used with ink and pigments:
(1) control, (2) gold color, (3) red color, (4) black ink, and (5) blue color.
100
100
100
100
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Fig. 6. Microscopic pictures of vegetable tanned leather bookbinding: (A) shrinkage temperature of the sample at room temperature at 22 C, before
shrinkage; (B) shrinkage activity of individual bers at 48 C; (C) shrinkage activity in more than one ber at 55 C; (D) shrinkage activity in some bers at
59 C; (E) the nal shrinkage activity at 64 C; (F) shrinkage temperature measurement of different sample of the leather bookbinding.
Fig. 7. Identication of animal skin: (A) goat skin (after Haines, 1981), (B) goat skin from the historical bookbinding.
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Fig. 8. HPLC elution prole: (A) New tanning material extracted from Acacia Arabica. (B) Tanning material extracted from vegetable-tanned bookbinding.
Table 2
Chemical analysis of paper.
Samples
Original paper
Restoration paper
Interior lining paper
Exterior lining paper
Components (%)
a-cellulose
Lignin
Ash
57.0
38.9
22.5
35.9
0.8
4.2
10.7
6.8
1.3
2.8
4.2
3.4
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