Tracking Colour - Preliminary Report 1 (2009)

Title: Tracking Colour. The polychromy of Greek and Roman sculpture in the Ny Carlsberg Glyptotek. Preliminary Report 1

Editor: Jan Stubbe Østergaard and the Copenhagen Polychromy Network

Publisher: Ny Carlsberg Glyptotek & the Copenhagen Polychromy Network

Year: 2009

Pages: 98

ISSN: 1904-1888

Link: http://www.glyptoteket.dk/... (PDF , 3.79 Mb)

From the Preface:

From 2004 to 2008, the Ny Carlsberg Glyptotek and the Copenhagen Polychromy Network (CPN) carried out a Pilot Project in the museum’s collection of Greek and Roman sculpture. In June 2008 we started the so-called Main Project which will run until 2011. The first phase of visual examination began in January 2009 and lasted until this summer. Some provisional results of these activities are published in this first Preliminary Report. The Report also contains an introduction to the CPN and outlines of both the Pilot Project and the Main Project. The protocol followed in visual examination and documentation is not the subject of a separate article, but is presented instead as applied in practise. [...]

Table of Contents:

Introducing the Copenhagen Polychromy Network, Jan Stubbe Østergaard

The Copenhagen Polychromy Network pilot project 2004–2008

The CPN Pilot Project: a brief introduction and evaluation, Jan Stubbe Østergaard

Investigating the polychromy of a Classical Attic Greek marble female head NCG IN 2830, Mikkel Scharff, Rebecca Hast, Nicoline Kalsbeek, Jan Stubbe Østergaard

Preliminary results from geochemical analysis of pigments on ancient Greek & Roman marble sculptures, Minik T. Rosing and Jan Stubbe Østergaard

Raman spectroscopy characterization of colored pigments in archaeological materials, Rolf W. Berg

The Copenhagen Polychromy Network main project 2008–2011

The CPN Main Project 2008–2011: an outline, Jan Stubbe Østergaard

Documentation and investigation of traces of colour on the Archaic Sphinx NCG IN 1203, Maria Louise Sargent, Lin Rosa Spaabek, Mikkel Scharff, Jan Stubbe Østergaard

Advances in Raman mapping of works of art (2010)

Title: Advances in Raman mapping of works of art
Authors: Polonca Ropret, Costanza Miliani, Silvia A. Centeno, Crtomir Tavzesab and Francesca Rosi
Citation: Journal of Raman Spectroscopy (Special Issue: Raman spectroscopy in art and archaecology), Volume 41, Issue 11, pages 1172–1177, November 2010

Link: http://hdl.handle.net/... (pdf, 553 Kb)


Abstract

Raman mapping can provide molecular information to complement data derived from other analytical techniques in works of art and other objects of cultural significance. Raman mapping can be performed using a motorized microscope stage that moves a sample or an object point by point in two spatial directions. The method can be used both noninvasively in works of art that fit under a microscope objective and in microsamples when, for example, obtaining information on the samples' layering structure is necessary. This paper reports on the development of a Raman mapping approach based on a set of scanning mirrors that direct the laser beam in two spatial directions, vertically through the microscope head or through a horizontal exit on the Raman microspectrometer. The first configuration still has limitations in terms of the size of the work of art that can be analyzed, as it has to fit under the microscope objective, but considerably larger objects can be studied when using the scanning mirrors placed in the horizontal exit. In this paper, the advantages and limitations of these two Raman mapping approaches are compared and discussed on the basis of an example of a contemporary oil painting on canvas.

Article: Analysis of South-Asian Shaman paintings (2008)

Title: Analysis of South-Asian Shaman paintings at the national museum of Denmark
Author: P. Vandenabeele, M. C. Christensen, L. Moens
Reference: Journal of Raman Spectroscopy, Volume 39 Issue 8, 2008, Pages 1030-1034
Link: http://hdl.handle.net/... (pdf, 193 Kb)

Abstract:

Raman spectroscopy is often used for the non-destructive analysis of archaeological objects or artefacts. Recently, the use of mobile Raman instrumentation has become increasingly popular for in situ investigations. Moreover, in this work, direct Raman analysis was completed with Fourier-transform infrared (FT-IR) analysis and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX). We used a dedicated mobile Raman instrument to perform direct analysis on a series of Shaman paintings on textile, which are part of the collection of the National Museum of Denmark. In general, relatively little attention has been given to the investigation of 19th or 20th Century artworks of Southeast Asian origin. The paintings under investigation depict Shaman gods and were previously dated between 1870 and 1950. The aim of this work was to obtain information on the materials that were applied and to narrow these dates, based on the artists' materials that could be identified. By using the combination of analytical techniques (Raman analysis with FT-IR and SEM-EDX), it was possible to obtain information on inorganic and organic pigments, the binding medium and the canvas.

Article: Micro-Raman spectroscopy of pottery (2010)

Title: Micro-Raman spectroscopy of decorated pottery from the Iberian archaeological site of Puente Tables (Jaén, Spain, 7th - 4th century B.C.)
Authors: D. Parras, P. Vandenabeele, A. Sánchez, M. Montejo, L. Moens and N. Ramos
Reference: Journal of Raman Spectroscopy 41, 2010, 68-73
DOI: 10.1002/jrs.2405
Link: http://hdl.handle.net/... (pdf, Mb)

Abstract:
In this paper, Raman spectroscopy is used for the first time to identify the pigments on decorated antique Iberian pottery. Ceramic fragments of type Real and others from the archaeological excavation in the oppidum Puente Tablas were examined. Different types of iron oxide pigments (hematite and goethite) were identified, along with amorphous carbon. in some samples, the presence of chalk or gypsum could be demonstrated. Some unattributed Raman bands are believed to be associated either with post-burial organic deposition or with silicate materials that are present in red ochre. It was possible to relate the findings with geological data from the region and to make assumptions on a local production.

Thesis: Raman spectroscopy applied to iron oxide pigments (2008)

Title: Raman spectroscopy applied to iron oxide pigments from waste materials and earthenware archaeological objects
Author: Malebogo Andries Legodi
University: University of Pretoria
Year: 2008
Type of Document: PhD Thesis
Link: http://up.ac.za/... (pdf)

Abstract:

Raman spectroscopy is a vibrational spectroscopic technique. It gives a unique combination of non-destructive analysis, high spatial resolution and phase characterisation. In the current study Raman spectroscopy was used as the primary technique during the study of chemical components in archaeological earthenware samples (i.e. low temperature fired clay pottery) of South African and Chinese origin, and characterisation of iron oxides derived from mill scale. One shard from each of the South African archaeological sites (Rooiwal, Lydenburg, Makahane and Graskop) was analysed by Raman spectroscopy, FT-IR spectroscopy, X-ray fluorescence (XRF) spectroscopy and X-ray diffractometry (XRD). The common features observed were montmorillonite (Mg3(Si,Al)4(OH)2.4.5H2O[Mg]0.35), kaolin (Al2Si2O5(OH)5), quartz (α-SiO2), feldspar (K- and NaAlSi3O8), hematite (α-Fe2O3), calcium silicate (CaSiO3) and illite (KAl4(Si7AlO20)(OH)4). Gypsum (CaSO4.2H2O) and calcium carbonates (CaCO3) were detected in Lydenburg, Makahane and Graskop shards. Amorphous carbon was observed in Lydenburg and Makahane shards while rutile appeared only in Makahane shard. The Lydenburg and Rooiwal shards showed the presence of anhydrite (CaSO4). The Chinese clay samples investigated by Raman spectroscopy were from the J A Van Tilburg museum at the University of Pretoria. The large red shard was recovered from the 1552 Portuguese shipwreck, São João, found around Port Edward, South Africa. Four other shards (two red and two gray) were recovered from the 1622 Portuguese shipwreck, the São João Baptista, found around Kenton-on-Sea off the South African coast. A 19th century Chinese teapot was also analysed. Hematite, kaolin, quartz, amorphous carbon and aluminosilicates were observed in all three red shards. All these components, except quartz, were also observed in the teapot. The gray shards showed the presence of quartz, kaolin, amorphous carbon and aluminosilicates. The pigments identified were hematite (in red samples) and black amorphous carbon (in all samples). Magnetite and goethite were precipitated from mill scale-derived precursors in aqueous media. Hematite was then prepared from the calcination of goethite at 750°C and maghemite from the thermal treatment of magnetite at 200°C. The iron oxides were characterised by Raman spectroscopy, XRD, surface area determination and scanning electron microscopy (SEM). They were generally composed of very small sized particles showing high surface area values.

Table of contents (short version):
1. Overall Introduction
2. Literature Review
3. Raman Spectroscopy
4. Raman Spectroscopy study of ancient South African domestic clay pottery
5. Raman analysis of red-brown and gray shards from 16th and 17th century Portuguese shipwrecks
6. The preparation of magnetite, goethite, hematite and maghemite of pigment quality from mill scale iron waste
7. Overall conclusion

Thesis: Raman spectroscopy of nanomaterials: applications in Archaeology

Title: Micro-Raman spectroscopy of nanomaterials: applications in Archaeology
Author: Linda Charlotta Prinsloo
University: University of Pretoria
Year: 2008
Type of Document: PhD thesis
Link: http://up.ac.za/... (pdf)

Abstract:

“Nanomaterials” is a generic term used to describe nano-sized crystals and bulk homogenous materials with a structural disorder at the nanoscale. Ancient (and modern) ceramics and glasses derive some of their properties (eg. pliability and low sintering temperature) from the fact that their raw material namely natural clay is nanosized. Furthermore the pigments used to colour ceramics and glasses need to have particle sizes 500 nm for the object to appear homogenously coloured to the human eye. Raman spectroscopy intrinsically probes chemical bonds and is therefore one of the few techniques that has been proven useful to provide information at the nanoscale. It is an excellent tool to study ceramics and glasses as a Raman spectrum can be used to identify phases, analyse amorphous domains in the silicate network and identify pigments on a nano-scale. The characteristics of a glass, ceramic or ceramic glaze derived through its Raman spectrum can then be linked to the technology used to produce an artefact and in this way provide information about its relative age and provenance. Likewise, the identification of pigments and binders in San rock art might provide information about production techniques and assist in the developement of conservation procedures. In this thesis micro-Raman spectroscopy (with X-ray fluorescence, X-ray powder diffraction, electronmicroscopy and photoluminescence as supportive techniques) was utilised to study archaeological artefacts from the Mapungubwe Collection and San rock art. It was possible to re-date celadon shards excavated on Mapungubwe hill in 1934 to the Yuan or even later Ming dynasty in stead of its original classification as Song. A profile of the glass technology used to produce the Mapungubwe oblates, small trade beads from the “royal burials” on Mapungubwe hill was determined and quite a few unique characteristics of the beads may eventually help to establish their provenance. The possible influence of the presence of rock hyraces at rock art sites on the deterioration of rock art were investigated and during the study very rare polymorphs of CaCO3 (vaterite and monohydrocalcite) were discovered in rock hyrax urine. This study was extended to analyse a San rock art fragment and another first was the identification of animal fat on the fragment, but the exact origin of the fat has to be verified by similar experiments.

Table of contents (short version):

1. Introduction
2. Theoretical Background
3. Re-dating of Chinese celadon shards excavated on Mapungubwe Hill, a 13th century Iron Age site in South Africa, using Raman spectroscopy, XRF and XRD
4. A Raman spectroscopy study of the Mapungubwe oblates; glass trade beads excavated at an Iron Age archaeological site in South Africa
5. Rock hyraces: a cause of San rock art deterioration?
6. The first Raman spectroscopy study of San rock art in the uKhahlamba Drakensberg Park, South Africa
7. Conclusions

Physico-Chemical Research of Cultural Heritage Materials Using Microanalytical methods (2009)

Title: Physico-Chemical Research of Cultural Heritage Materials Using Microanalytical methods
Author: Liz Karen Herrera Quintero
Advisors: Ángel Justo Erbez and José Luis Pérez Rodríguez
Publisher: Instituto de Ciencia de Materiales de Sevilla (ICMS-CSIC), Universidad de Sevilla
Pages: 223 pages
Year: 2009
ISBN: 846920906-X
Type: Doctoral thesis
Site: http://hdl.handle.net/...

Abstract:

The research work included in this thesis is focused on the characterisation of five different materials: paintings, baroque mirrors, natural fibres, organ pipes and several metallic artefacts, which are representative of Spanish Cultural Heritage. All of these ornamental elements are characteristic of the Andalusian Baroque period of art. One of the main contributions of this work is the application of synchrotron radiation-based techniques at the European Synchrotron Radiation Facility (ESRF) within the Cultural Heritage Group. These synchrotron x-ray techniques were carried out in combination with other analytical laboratory techniques such as x-ray diffraction, micro-infrared, micro-Raman spectroscopy, optical and electron microscopy, and mass spectrometry. Synchrotron radiation was very powerful and useful in the detection, analysis and distribution of different elements and crystal phases. These findings are critical to the different aspects of the artwork.

Index (short version):

Chapter I. Studies and Research of Paintings
I.1. Advanced Combined Application of μ-X-ray Diffraction/μ-X-ray Fluorescence with Conventional Techniques for the Identification of Pictorial Materials from Baroque Andalusia Paintings
I. 2. Characterisation of iron oxide-based pigments by micro X-Ray diffraction
I. 3. Synchrotron-based X-ray experiments used for the study of an iron oxide micrometric pigment in 18th century paintings
I. 4. Characterisation of azurite and malachite pigments by combined application of μ-X-ray diffraction/μ-X-ray fluorescence in cross section from Spanish Baroque paintings

Chapter II. Studies on Ancient Mirrors
II.1. Hg/Sn amalgam degradation of ancient glass mirrors
II.2. Study of nanocrystalline SnO2 particles formed during the corrosion processes of ancient amalgam mirrors

Chapter III. Studies on Baroque Metallic Organ Pipes
III.1. Chemical composition of the metal pipes of Spanish baroque organs as determined by laboratory and synchrotron techniques
III.2. Chemical composition of the red pipes of a Spanish baroque organ

Chapter IV. Studies of Ancient Fibres
IV. Identification of cellulose fibres belonging to Spanish cultural heritage using synchrotron x-ray diffraction and laboratory techniques

Chapter V. Studies of Metallic Artefacts
V. Analysis of cultural heritage metallic artefacts from Andalusia

Chapter VI. Conclusions
Chapter VII. Resumen