Aplicaciones de las espectroscopías IR y Raman al Patrimonio

Transcripción

Aplicaciones de las espectroscopías
IR y Raman
al Patrimonio Histórico y Cultural
Concepción Domingo
Instituto de Estructura de la Materia, CSIC
28006 Madrid, Spain
Spectrum
I
λ (nm)
E
?
Raman and IR Transitions
Raman
IR Absorptions
Energy Levels of CO2
Raman
\\
Energy,, Difference cm-1
Energy
20,000
?3
2350
?1
1335
667
Zero Pt
?2
IR
IR
Vibrations of CO2
No dipole change
Dipole change
Dipole change
% Transmission
IR and Raman Spectra of CO2
Infrared
spectrum
Scattering Intensity
4000
2000
0
Raman
spectrum
4000
2000
Wavenumber (cm-1)
0
Análisis de materiales para determinar:
- Producción y métodos (análisis)
- Deterioro (cambios)
-Conservación (asesorar)
“Scientific Examination of Art:
Modern Techniques in Conservation and Analysis”
(Sackler NAS Colloquium),
Proceedings of the National Academy of Sciences, 2005
http://www.nap.edu/catalog.php?record_id=11413
Objetos del Patrimonio
- Desde cañones sumergidos en el mar hasta miniaturas de marfil
- Piedra, papel, metal, textiles, vidrio, …
- Sustratos, Pigmentos, aglutinantes, conservantes, consolidantes, …
-
IR-spectra
PROTEINS
Bone glue (from collagen)
Polyamide
Fish glue (gelatin)
OILS
CARBOHYDRATES
Linseed oil
Starches (C6H10O5)n.
PROTEINS
Beeswax
70 % higher aliphatic esters,
13 % free wax acids
12% hydrocarbons
NATURAL RESINS
Turpentine C10H16, Turpentine is commonly used as a thinner or diluent
for oil paints and varnishes and as a raw material for the chemical industry
Colophony
SYNTHETIC RESINS
Acrylate
Latex
Ph. Colomban, M.-P. Etcheverry, M.
Asquier, M. Bounichou, A. Tournié.
« Raman Identification of Ancient Stained
Glasses and their Degree of Deterioration »
J. Raman Spectrosc. 37 (2006).
LA SAINTE CHAPELLE (PARIS)
La revue de la céramique et du verre,
148, 18-21(2006)
http://www.eu-artech.org/
MOLAB
MOBILE LABORATORY
10 instruments are available
- fibre-optics FTIR
-micro Raman
- fibre-optics UV fluorescence spectrometry
- fibre-optics Vis-NIR spectrometry
- scanning IR reflectometry
- laser micro-profilometry
- XRF
- fluorescence spectrometry
- NMR tomography
- DRMS
MOL
AB
M
1
Examination of "Lamentation over the dead
Christ" by Agnolo Bronzino
July 04
Musée des Beaux-Arts et
d'Archéologie - BESANCON France
MOL
AB
M
2
Composition and structure of lustre
decorations on original Italian Renaissance
lustreware
March 05
Victoria & Albert Museum LONDON - United Kingdom
MOL
AB
M
3
A technical study of Leonardo’s "Virgin of the
Rocks" and associated Leonardesque
paintings
March 05
National Gallery - LONDON United Kingdom
MOL
AB
M
4
Investigation of the St. Euthymios chapel
wall paintings at the Basilica of St. Demetrius
in Thessaloniki.
MarchApril 05
Archaeologic Institute of
Macedonia & Thrace THESSALONIKI - Greece
MOL
AB
M
5
Scientific non-destructive examination of
Leonardo paintings in The Hermitage
Museum
May 05
Hermitage Museum - SAINTPETERSBURG - Russia
MOL
AB
M
6
Study of the painting technique of Johann
Baptist Lampi, father and son, at the
Moravian Gallery in Brno
June 05
Institute of inorganic chemistry
- Academy of Science of Czech
Republic-PRAGUE
MOL
AB
M
7
The Four Gospels Book from Humor
Sept 05
National Art Museum of
Romania BUCHAREST Romania
MOL
AB
M
8
Non-invasive analysis of materials from
paitings by Paul Cezanne in the Courtauld
Institute Gallery, London
Dec 05
Courtauld Institute of Art,
Department of Conservation
and Technolgy LONDON United Kingdom
MOL
AB
M
9
Investigation of silver tarnish risk and
remaining protection afforded by lacquers
Jan 06
English Heritage - LONDON United Kingdom
MOL
AB
M
1
0
The Macclesfield Psalter & Metz Pontifical
Jan 06
Hamilton Kerr Institute, Uni of
CAMBRIDGE - United
Kingdom
MOL
AB
M
1
1
In-situ identification of the penetration depth
of consolidants on bioclastic limestones
through micro-drilling measurements
Apr 06
25th Ephorate of prehistoric
and classical antiquitiesATHENS - Greece
MOL
AB
M
1
2
Analysis of polychromies and of the effects
of consolidation in the stones of the facades
of the Cathedral and Provincial Museum of
Huesca, Spain
Apr 06
Uni OVIEDO - Institute of
Petrology - Spain
MOL
AB
M
1
3
Comparative characterisation of two
medieval codex of the 12 th Century and
damage assesment of the parchment
support
May 06
Instituto do Arquivos Nacionais
- TORRE DO TOMBO Portugal
MOL
AB
M
1
4
Casas pintadas de Evora
May 06
Instituto Portugues de
Concervaçao e Restauro LISBOA - Portugal
MOL
AB
M
1
5
Drawing and colour in designing a painting :
Polidoro artwork in Capodimonte
May 06
Sopritendenza speciale per il
polo museale di NAPOLI - Italy
MOL
AB
M
1
6
A technical study of the paintings "Amor
vincit omnia" by Caravaggio, "Portrait of a
lady (Dorotea)" and "Reclining nude of a
woman in a landscape (Cerere)" by
Sebastiano del Piombo
June 06
Gemäldegalerie- Staatliche
Museen zu BERLIN - Germany
MOL
AB
M
1
7
Paint on early Meissen Stoneware
June 06
Staatliche Kunstammlungen
Dresden - Porzellansamlung
DRESDEN - Germany
MOL
AB
M
1
8
Study of gemstones, metal alloys and
enamels in historical jewellery at the Victoria
and Albert Museum, by non-destructive
techniques
Oct 06
Victoria and Albert Museum
LONDON - United Kingdom
MOL
AB
M
1
9
Art technological research toward the Victory
Boogie Woogie (1942-1944) by Piet
Mondriaan
Gemeentemuseum DEN HAAG
- The Netherlands
MOL
AB
M
2
0
Study of the composition and structure of
lustre decorations on original Italian
Renaissance lusterware at the Wallace
Collection
Wallace Collection LONDON United Kingdom
MOL
AB
M
2
1
Study of surface layers and other
substances applied in the past on the Parian
and Pentelic marbles of the Greek sculpture
of Esculapio from Empúries (Girona): control
of cleaning methodologies
Museu Nacional d’Art de
Catalunya (MNAC) Restoration and Preventive
Conservation Department
BARCELONA - Spain
http://www.eu-artech.org/files/UserReportBurgio.pdf
Project: Study of the composition and structure of lustre decorations on
original Italian Reinassance lustreware
User Group Leader: Lucia Burgio
Location: Victoria and Albert Museum, London, United Kingdom
http://www.eu-artech.org/files/UserReportStoulig.pdf
Project: Study of the painting Lamentation on the dead Christ
by Agnolo di Cosimo di Mariano, called Il Bronzino, 1545
User Group Leader: Claire Stoulig
Location : Musée des Beaux Arts et de Archeologie, Besançon, France
FT-IR spectra collected on whitish and yellowish lacunas present in the lower part of the painting
showed particular absorptions at 2135, 2235, 2304, 2378 cm-1 together with a band at 1207 cm-1
characterized by a reststrahlen shape. They have been compared with the reflectance spectrum
of a typical protein, animal glue, presenting all the main features of this substances:
amide I-1670 cm-1, carbonyl stretching vibration;
amide II-1580cm-1, combination of CN and NH vibrations;
amide III-1470 and 1406 cm-1,
CH bending vibrations
MOLAB at the Musée des Beaux Arts et de Archeologie, Besançon, France
http://www.eu-artech.org/files/User%20Report%20MOLAB_Putna.pdf
Project: Romanian illuminated medieval manuscripts – Scientific research on the
materials and techniques
User Group Leader: Mihai Lupu,
National Art Museum of Romania , Bucharest, Romania
Location: Monastery of Putna, Suceava County, Romania
Research on the materials and techniques was carried out using
the following MOLAB in-situ techniques:
XRF, micro-Raman, fiber-optic Mid FT-IR and NIR
Carbono
Intensidad Raman (u.a.)
Bermellón
Yeso
200
400
600
800
1000 1200 1400 1600 1800
-1
Números de onda/cm
Arqueta 2
200
300
400
-1
Números de onda/cm
Arqueta 1
Cara frontal
Rojo Amarillo Negro
* Oropimente (As2S3)
*
*
**
* *
Carbono
*
*
*
C
**
*
Fosfato (PO ) *
C
L
L: Lignina
C: Celulosa
"Cal" (soporte)
**
I Anhidrita (CaSO4)
*
34
I I
L
I
C
L
L
C C
L
C
I I
C
L
L
L
**
400
600
800
200
1000 1200 1400 1600 1800
Números de onda/cm
-1
400
600
800
1000 1200 1400 1600 1800
Números de onda/cm
Lateral con figuras: San Juan
Corona
Cara
Azul
Verde
400
I
0,1
I
*
*
*
"Cal"
*
Yeso
Oropimente (As2S3)
1100
Indigo (C16H10N2O2)
*
Indigo (C16H10N2O2)
*
*
* *
200
400
600
800
1000 1200 1400 1600 1800
-1
Números de onda/cm
2800
Interior de la tapa
Fondo azul oscuro
Estrellas amarillas
I
"Cal"
*
1600
-1
I
1000
1200
Números de onda/cm
I Anhidrita (CaSO4)
* Bermellón (HgS)
* Oropimente (As2S3) I Yeso (CaSO4.2H2O)
I Blanco de plomo (2PbCO3.Pb(OH)2)
* Carbono
800
-1
200
* Carbono
Madera
* Bermellón (HgS)
*
* Bermellón (HgS)
200
400
600
800 1000 1200 1400 1600 1800
-1
Números de onda/cm
3200
RESULTADOS
De los resultados de los análisis Raman y de los estudios estilísticos se concluye
que la “Arqueta 1” perteneciente sin duda a finales del siglo XIV, presenta los
pigmentos puros, utilizando una finísima capa de yeso como imprimación,
mientras que el resto que estilísticamente pertenece a los últimos años del siglo
XVII o principios del XVIII, ha utilizado diversos componentes de origen
orgánico como puede ser el lienzo y el óleo y que incluso la pintura aplicada en
toda ella, resulta ser anterior a 1900, ya que se advierten los mismos elementos,
sin restauraciones pictóricas modernas.
La “Arqueta 2”, pese a las dificultades expuestas por el manejo físico, al
presentar el mismo bermellón, nos permite fecharla antes de finales del siglo
XIX, aunque como ya se ha dicho anteriormente el análisis estilístico y visual
de los elementos imposibilita su adscripción al siglo XVI, en que estaba datada.
* Carbon
* Laurionite
* Litharge
* Anglesite
* Hydrocerrusite
* Massicot
*
* Phosgenite * Hydrocerrusite
* Laurionite * Cerrusite
Carbonatos "mixtos"
*
**
*
**
*
**
P-5
P-3a
P-3b
* *
*
400
*
*
*
1000
600
800
*
A-6
1050
1100
**
*
A-4b
*
*
*
C-1b
200
** *
* *
*
C-1a
*
* Calcita
*
A-8a
*
* *
A-8b
1000 1200 1400 1600 1800
-1
Números de onda /cm
200
400
600
800 1000 1200 1400 1600 1800
-1
Números de onda /cm
Possibilities of the molecular Infrared and Raman spectroscopies to monitor the
polymerization process of water repellents and consolidants in treated stones
(collaboration with the IEG group of the TNCH )
3 months
2 days
2000
1500
1000
500
4000
Wavenumbers / cm
Tegosivin (10% wt in White Spirit) / KBr
IR Absorbance (a.u.)
2 days
2 hours
11 min
** *
1500
2 days
1 hour
1000
-1
Wavenumbers / cm
Tegosivin over glass
2 months
5 days
2 days
2 hours
1 hour
3000
2000
3000
1000
2800
νSi-O-Si δ C-Si-C
3100 3000 2900 2800
1600 1400 1200 1000 800 600 400 200
500
IR Transmission spectra of
the
products
squeezed
between KBr disks.
The IR reflection of the stone
had a very strong calcite
band which prevented from
observing the silane-based
compounds bands.
FT-Raman spectra of the impregnated
stones excited at 1064 nm showed
strong calcite bands, but the detailed
study of the C-H stretching region
allowed to conclude:
1) The evaporation of the White Spirit
employed as solvent in the waterrepellent case, finished 14 days after
application. This period coincides with
the largest loss of weight of the
corresponding specimen.
2) The decrease with time of the
integrated intensity of the marked
region in the consolidant case showed
a trend which someway correlated
with the loss of weight directly
measured, specially from the 14 day
on. Then, our Raman data support the
“weight control” as good choice for
indication of curing.
1
0
6
4
600
400
200
Wavenumbers / cm
Raman Microscope 50X
λlaser = 785 nm
The strong fluorescence of the
biocalcarenite stone at 785 nm
made impossible to detect the
spectra of the consolidant and
of the water-repellent on the
correspondingly impregnated
samples.
Stone/ Tegovakon
1400 1200 1000 800
-1
Wavenumbers / cm
Wavenumbers / cm-1
3 months
*
6 days
-1
-1
4000 3500 3000
*
Tegosivin (10% wt in White Spirit) over glass
5 days
Raman Intensity (a.u.)
2500
2 days
Tegovakon over glass
2 days
2 hours
3000
28001600 1400 1200 1000 800 600 400 200
-1
Wavenumbers / cm
Stone/ Tegosivin 10 wt in WS
42 days
42 days
n
28 days m
16 days
14 days
11 days
9 days
7 days
3000
3 months
3500
Tegosivin modified (Silo) solid (>1 year)
1 min
10 min
4000
Tegovakon solid (2 years)
Tegovakon / KBr
Tegosivin / KBr
The increasing use of portable instruments, also Raman and infrared spectrometers, for in situ
diagnosis and characterization of materials and their conservation state in artworks, has led us
to investigate the real possibilities that both vibrational spectroscopies have for monitoring in
real time the polymerization process of silicon-based water repellents and consolidants in
stones after application of the corresponding treatments. A particular stone (biocalcarenite)
widely used in the Spanish Architectural Heritage, has been chosen as laboratory model stone.
28 days
16 days
14 days
11 days
9 days
7 days
4 days
4 days
2 days
2 days
initial
initial
3000 2800
1600 1200
800
Wavenumbers / cm
400
-1
3000 2800
1600 1200
800
Wavenumbers / cm
400
-1
"IV International Conference on the Application of Raman Spectroscopy in
Art and Archaeology",
http://www.chimica.unimore.it/RAA2007/raa2007.htm
----------------------------------------------------------------------------"Raman spectroscopy in art and archaeology"
J. Raman Spectrosc. 2006; 37: 962–965
Procc. III International Conference on the Application of Raman Spectroscopy in Art and
Archaeology
-----------------------------------------------------------------------------http://www.nap.edu/catalog.php?record_id=11413
(Sackler NAS Colloquium) Scientific Examination of Art:
Modern Techniques in Conservation and Analysis,
Proceedings of the National Academy of Sciences, 2005
http://books.nap.edu/openbook.php?isbn=0309096251&page=162
Raman Microscopy in the Identification of Pigments on Manuscripts and Other Artwork,
R.J.H. CLARK
162-185
------------------------------------------------------------------------------Smith GD, Clark RJH
Raman microscopy in archaeological science
JOURNAL OF ARCHAEOLOGICAL SCIENCE 31 (8): 1137-1160 AUG 2004
-------------------------------------------------------------------------------
http://www.chem.ucl.ac.uk/resources/raman/index.html
--------------------------------------------------------------Raman Microscopy Research in The British Library
The analysis of materials used in the making and for the conservation of manuscripts
incunabula and works of art
http://www.bl.uk/about/collectioncare/pdf/raman.pdf
----------------------------------------------------------------Raman microscopy techniques for the characterisation of pigments
Tracey D. Chaplin, & Robin J. H. Clark
http://www.rms.org.uk/downloads/5_-_Chaplin-Clark.pdf
-----------------------------------------------------------------http://www.chim.unifi.it/raman/
-----------------------------------------------------------------Database of Raman spectroscopy, X-ray diffraction and chemistry of minerals
http://rruff.info/
-----------------------------------------------------------------www.? s.unipr.it./~bersani/raman/raman/spettri.htm
-----------------------------------------------------------------www.sbg.ac.at/min/service/service_daten.htm
------------------------------------------------------------------www.ens-lyon.fr/LST/Raman/index.php
------------------------------------------------------------------minerals.gps.caltech.edu/FILES/raman/Caltech_data/index.htm
The application of Raman Spectroscopy for the Non-destructive Analysis of
Art Objects
http://www.ndt.net/article/wcndt00/papers/idn163/idn163.htm
"Identification and Classification of Natural Organic Binding Media and
Varnishes by Micro-Raman Spectroscopy
http://www.ndt.net/article/wcndt00/papers/idn164/idn164.htm
Peter Vandenabeele and Luc Moens
---------------------------------------------------APPLICATION OF RAMAN TECHNIQUES
FOR PAPER COATINGS
Shivashanker Bitla
http://www.library.umaine.edu/theses/pdf/BitlaS2002.pdf
--------------------------------------------------CONFOCAL RAMAN MICROSCOPY IN CHEMICAL AND
PHYSICAL CHARACTERIZATION OF COATED AND PRINTED
PAPERS
Jouko Vyörykkä
http://lib.tkk.fi/Diss/2004/isbn9512272318/isbn9512272318.pdf
minerals.gps.caltech.edu/FILES/raman/Novosibirsk_Russia/Index.htm
----------------------------------------http://www.aist.go.jp/RIODB/SDBS/cgi-bin/direct_frame_top.cgi?lang=eng
Spectral Database for Organic Compounds SDBS
--------------------------------------------FT-IR SPECTRA OF BINDERS AND COLORANTS
http://www.ut.ee/katsekoda/IR_Spectra/
--------------------------------------------www.aist.go.jp/RIODB/rasmin/E_index.htm
---------------------------------------------www.irug.org
----------------------------------------------newton.mli.kvl.dk/users/engelsen/specarb/specarb.html (Carbohidratos)
-----------------------------------------------
ESPAÑA
http://goya.fmc.cie.uva.es/Pigmentos/inicio.htm
- Colorimetría (CR)
- Difracción de Rayos X (DRX)
- Espectroscopía µRAMAN
- Espectroscopía FTIR(ATR)
--------------------------------http://www.ehu.es/udps/database/database.php
http://www.ehu.es/udps/database/database1.html

Aplicaciones de las espectroscopías IR y Raman al Patrimonio

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