Book of Abstracts

5th I erna a: on tbe appUcatJon o,f Raman spectrosco y in Art and ~rchaeology

Bilbao (Spain)

14th - 18th September 2009

Juan Manuel Madariaga (ed.) . 7. a • ..,."" •. 1 .~

----

Universidad Euskal Herriko del PaIs Vasco Unibertsitat911

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ogy

5th International Congress on the Application of Raman Spectroscopy

in Art and Archaeology Book of Abstracts

Bilbao (Spain)14th -18th September 2009

Juan Manuel Madariaga (ed.)

Universidad Euskal Herriko del País Vasco Unibertsitatea

ARGITALPE.N ZERBITZUA SERVICIO EDITORIAL

Poster presentations

Raman spectroscopic analysis of a potentially important Howell G.M. Edwards Renaissance painting

As beautiful as the woman in Ancient Rome : an Eisa Van Elslande overview of theRaman studies on cosmetic powders from Pompeii

Comparison of the palettes of two medieval Italian Maurizio Aceto scriptoria by non invasive techniques

Characterization of two pairs of 16th century Nanbam Sofia Pessanha folding screens

Micro-Raman and X-Rays Fluorescence Spectroscopy Adrian Duran Benito as non destructive techniques for pigments and dyestuffs identification in an Arabic illuminated manuscript

Minerals from Macedonia. XXVI. Vibrational spectroscopic characterization of grossular and uvarovite

Raman description of indigoid hybrid colorants

Verdigris pigment: a mixture of compounds. Input from Raman spectroscopy

Evaluation of micro-Raman for imaging of lake pigment distribution in varnish

Raman analysis of the mediaeval manuscript 'Liber Floridus' at the library of Ghent University

Pigment characterisation of Finnish wallpapers of the XVIII-XIX century: comparison with those used in western Europe

Surface-enhanced Raman Scattering of quinacridone quinone pigment employing Calixarenes as dispersive cavitands

Analysis with ATR-Far Infrared Spectroscopy of natural resins used as paint varnishes

Raman spectroscopy characterization of charcoal in tongues and shallots of reed pipes from historical baroque organs

The identification of ancient textile dyes by surface­enhanced Raman spectroscopy (SERS) on silver and gold colloids

Raman spectroscopic investigation on historical glass in Thailand

Raman spectroscopy used to study gamma-irradiated painted wood panels

Pigment Lead Tin Yellow Type 11 in yellowish tesserae of Spanish Roman Mosaics

Study oftwo Oriental illuminated manuscripts (16th century) using micro-Raman spectroscopy

Polymer coatings for paper conservation: waterborne polyurethanes

Petre Makreski

Eisa Van Elslande

Margarita San Andrés Moya

Céline Paris

Annelien Deneckere

Kepa Castro

Elena del Puerto

Giorgia Sciutto

Liz Herrera

Federica Pozzi

Dararutana Pisutti

Maria Mihaela Manea

Javier Garcia Guinea

Tanevska Vinka

Aresatz Usobiaga

Po 2.1

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JUAN MANUEL MADARIAGA, President of the Organizing Committee of

the 5th International Congress on the Application of Raman

Spectrosc:opy in Art and Archaeology (RAA2009-Bilbao), --.--- ,,----------- - ----

CERTIFIES THAT

Javier Garcia-Guinea

has attended this Congress, held at the Fine Arts Museum of Bilbao from

14th September to 18th September 2009 in Bilbao (Spain).

In Bilbao, 18th September 2009.

lUAN MANUEL MADARlAGA

President of the Organizing Committee

Universidad Euskal Herriko del Pels \/asco Uniber1silalea

JUAN MANUEL MADARIAGA, President of the Organizing Committee of

the 5th International Congress on the Application of Raman

Spectroscopy in Art and Archaeology (RAA2009-Bilbao), certifies .-..- --

that the following Poster communication has been presented in the

Congress, held at the Fine Arts Museum of Bilbao from 14th September to

18th September 2009 in Bilbao (Spain):

Hyperspectral- and Thermo-Raman study of ornamental variscite

Authors: Prado-Herrero P., Garcia-Guinea J., Crespo-Feo E., Correcher V. and

Rubio J.

Code: Po 3.21

In Bilbao, 18th September 2009.

JUAN MANUEL MADARIAGA

President of the Organizing Commlttee

Universidad EllSlml Herriko del Pars Vasco Unlbertsitatea

JUAN MANUEL MADARIAGA, President of the Organizing Committee of

the 5th International Congress on the Application of Raman

Spectroscopy in Art_and Arctt~~QlogY-(BAA2Qº~.BiIºél.C))J. c~rt.ifi=es~ __

that the following Poster communication has been presented in the

Congress, held at the Fine Arts Museum of Bilbao from 14th September to

18th September 2009 in Bilbao (Spain):

Pigment Lead Tin Yellow Type 11 in yellowish

tesserae of Spanish Roman Mosaies

Authors: Crespo-Feo E., Garcia-Guinea J., Tormo L., Capel F., Caballero A., Ranz

1.

Code: Po 2.18

In Bilbao, 18th September 2009.

JUAN MANUEL MADARIAGA

President of the Organlzing Committee

Universidad Euskal Herriko del Pals Vasoo Unlbertsi lalea

Po 3.21

Hyperspectral- and Thermo-Raman study of ornamental variscite

Prado-Herrero P.a, Garcia-Guinea J .b, Crespo-Feo E.b,

Correcher V.a and Rubio J .c

·CIEMAT, Avenida Complutense 22, Edificio 2, Dosimetria de Radiaciones, E-28040 Madrid (Spain) bMuseo Nacional Ciencias Naturales - CSIC, Calle Jose GUlierrez Abascal 2, E-

28006 Madrid (Spain). ecrespo@mncn,csic.es ' Instituto Ceramica y Vidrio CSIC, Calle Kelsen 5, Campus Canloblanco, E-28049

Madrid (Spain)

Variscile is a hydraled aluminium phosphate wilh theorelical formula [AIP04 .2H20]. II shows a pale to deep 9reen colour due to Ihe substilulion of Cr> in A13> sites, This mineral is similar lo lurquoise and il can be easily cut and polished to obtain omaments such as necklaces or bracelets. Very importanl old mining activity has been described in Neolithic ages [Campubrl et al. , 2003; Dominguez-Bella, 20041 as well as in the Middle Age (Arribas etal., 19711 in the northeasl and northwest parts of Spain, respectively. The mined variscite from Ihese areas has been found as beads for necklaces in many Megalilh graves along southern Spain IAguayo de Hoyos and Garcia SanJuan, 2006] and in archaeological sites in Westem France [Querre el al., 2007]. In this las! paper, Ihe relationship belween Cr and V conlent is used for establishing the origin of the mineral. In Ihis sludy, we have analyzed a natural variscite for determining the distribution of Cr> and V3> in the mineral structure by means of hyperspectral Raman. In the same conlext, a Ihermo-Raman study has been performed for controlling the mineral stabili ly since hydrous phases tend lo be lransformed al temperatures as low as circa 60 oC. The sample, chemically analyzed by EPMA, gives rise a composition of P20 S -45,98%, AbO) ~33,97%, H20 - 19,56, Cr20) - 0.15% and traces elements (F, Ca, Zn, S, K and Sr). Figure 1 a shows Ihe hyperspectral-Raman líne-scan performed on Ihe variscile sample. The observed spectra agree with Ihe metavariscite features having the bands siluated below 700 cm·1 corresponding to the lallice modes (P04 out-of-plane bends and in-plane bends) and (P04 )$- anlisymmetric vibration bands localed al 1017 and 1077 cm' [Frost el al., 2004]. The presence of water in the melavariscile formula gives bands atthe second order Raman spectrum due to the OH strelching vibrations (31 19, 3369, and 3443 cm,l) as well as 1643 and 71 1 cm,l peaks corresponding to HOH bending and water vibration, respectively. Generally, pseudo-Iattice vibrations associated with aluminium can be seen in Ihe region of 740-570 cm,l for the anhydrous phase [Rokita el al. , 2000], Ihen Ihe alternated variations in the bands inlensity in bel10w 700 cm,l area can be related to alterations in the Al» bonds. It seems thal Cr> and V3> subslituted Al» are distributed as an altemalion of Cr or V-rich cluslers in the variscite structure. Figure 1b displays Ihe Thermo-Raman spectra obtained from room temperature up lo 50°C. In Ihis case, the mosl important change in the curves can also be observed in Ihe temperature inlerval 150 - 300 oC, Wilh Ihe increasing temperature, H20 relaled bands become weaker, disappearing completely al 300°C. II is worth lo observe Ihe alteration of bands 548, 578, 1017, and 1077 cm·1

, which also disappear al 300°C due lo Ihe melavariscite transformation to berlinite. The bending peak placed al -397 cm·1 loses inlensily after 150°C. After 300°C, most intense Raman vibration band~for Ihe new formed mineral are 1138 and 469 cm·1

. Olher authors [Rokila el al., 2000] report similar vibrations bands studying a berl inite from Hallsjoberg in Sweden.

Book of Abstracts: RAA2009 5th lotcmaliooal Conference DO lile applicalion ofRamao speclroscopy io Art aod Arcllaeology

Bilbao 14·18 September 2009 185

Po 3.21

Olher Ihermo-Raman works [Gregora el al., 20031, sludying AIPO. obtained by a hydrolhermal method, obtained oomparable results lo the here reported for Ihe same experimental window.

~ ... , .... t.·'-..e ~ ~ d • - ._..4f -..;

~::,== Wavenurnber(cm")

Figure 1: Hyperspectral-Raman showing the peaks inlensily varialion aloog a line­sean (a). In-sltu Thermo-Raman speclra In where II can be observed Ihe Iransformalion of Ihe variscile slruclure due to dehydration process.

The variscile behavlour along with temperalure records Ihe dehydralion process of Ihe hydrous phase forming Ihe anhydrous aluminium phosphate (berlinite). The obtained spectra display lhe answer of Ihe syslem under consideration, Irying lo accomm<Xlale Ihe new components of Ihe system (P, Al and 0 , without water) lo the changing physicochemical conditions, Le. Iooking for a more slable confguralioo Ihrough a progressive rearrangemenl of their components, moving forward up lo the berlinile slructure. Complementary lechniques document an importanl change in Ihe system behaviour circa 150-165 oC, which has been also mentioned in Ihe open literature as the transformation of metavariscite to berlinite. Additionally, Thermo­Raman analyses records the mos! importanl change al 300"C, showing clearly defined Ihe berlinile peaks Ihal remain present at higher temperatures.

Acknowledgements. This work has been partly financially supported by a JAE-Doc CSIC contracto

References Arribas A, Galan E, Martin-Pozas JM, Nicolau J, Salvador P. Stvdia GeoIogica 1971; 11:1 15.

Aguayo de Hoyos P, Garcia Sanjuan L, in Joussaume R, Laporte L, Scarre C.(Edilors), Origin and Oevelopment of the Megalithic Phenomenon of Westem Europe, Proceedings of the Intemational Symposium (Bourgon, Franca, Odober 26th-30th 2002), 2006, p. 452.

Camprubl A, Melgarejo J-C, Proenza JA, Costa F, Bosch J, Estrada A. Borell F, Yushkin NP, Andreichev VL. Episodes 2003; 26:295

Frost RL, Milis SJ, Erickson KL. Thermochimica Acta 2004; 419: 109.

Gregora 1, Magneroo N, Siman P, Luspin Y, Raimboux N, Phi1ippot E. Jouma/ o, Physic: Condensed Matter2003 ; 15:4487.

QUMe G, Herbault F, Galligaro Th. Proceedings o, lile X//ntemationa/ Conference 00 PIXE aOO ils Analytica/ applications (Puebla, Mexico, May 25-29) 2007; P II :38-1

Rokita M, Handke M, Mozgawa W. J. Mol. Struct. 2000; 555:351.

800k of Abslracls: RAA2009 5'" lntemational Confcrcnce on the applkation of Raman spcx:troscop)' in Art and Archaeolog)'

Bilbao 14·18 Septembcr 2009

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