ARRS project Z1-4404: Characterisation and stability of inks on paper

The overall objective of the project is to develop an analytical methodology for the proper characterisation and classification of inks (with a focus on carbon-based, iron-based and iron-Tannin, blue wood and sepia inks), present on selected works on paper of the Slovenian National Collections (National and University Library Due to the inestimable value of the selected objects, we will upgrade the analytical methods for minimally invasive and non-invasive measurements and for in situ analyses, and optimise the Surface Enhanced Raman Spectroscopy (SERS) procedure.) SERS will be complemented by other techniques that give elemental/molecular composition (such as X-ray fluorescence, infrared spectroscopy, electron paramagnetic resonance). This will allow us to address several aspects, such as the detection of trace components, the coordination of transition metals, the investigation of ink-paper interactions and the degradation. The spectral measurement datasets of the model samples will serve as a basis for accurate characterisation and classification of objects from the national collections. Experimental analyses will be combined with theoretical research (modelling), and this will serve as a basis for recommendations (guidelines) for the conservation of cultural heritage.

Data

Postdoctoral basic research project

Title: Characterisation and stability of inks on paper

Duration: 24 months (1.10.2022 - 30.9.2024)

Code: Z1-4404

Project leader: dr Klara Retko (SICRIS, ORCID, Google Scholar)

Financial resource: Public Agency for Research of the Republic of Slovenia (ARRS)

Content description

It is impossible to imagine today's world cultural heritage without the discovery of ink. Their use for writing, drawing and painting goes back centuries. Carbon-based inks are the oldest and probably the best known, but many others, such as iron-tannin, bluewood and sepia inks, are of equal historical importance. In heritage science research, their characterisation is extremely challenging, mainly due to their heterogeneity, the presence of inks in mixtures, limited sampling, ageing effects, etc. The lack of appropriate analytical methodology and optimised analytical tools for ink identification often leads to oversimplification of analytical results and to misinterpretations of technology. For example, in the case of iron-based bluewood inks, the materials are often misinterpreted as iron-tannin inks, while the mere absence of iron leads to the mislabelling of the materials as sepia or carbon-based inks. Such misinterpretations have a false impact on art-historical and technological evaluation, and can also provoke negative effects in heritage conservation and conservation procedures, especially in the case of chemical stabilisation, which is very often used for Iron-taninska inks. In addition, very little is known about the environmental impact on the stability of inks on paper. Currently, many versatile lighting systems are used by museums around the world. Any introduction of a new lighting system (e.g. white LED) requires an in-depth study of the impact of lighting on the photochemical degradation of inks.

The overall objective of the project is to develop an analytical methodology for the proper characterisation and classification of inks (with a focus on carbon-based, iron-based and iron-Tannin, blue wood and sepia inks), present on selected works on paper of the Slovenian National Collections (National and University Library Due to the inestimable value of the selected objects, we will upgrade the analytical methods for minimally invasive and non-invasive measurements and for in situ analyses, and optimise the Surface Enhanced Raman Spectroscopy (SERS) procedure.) SERS will be complemented by other techniques that give elemental/molecular composition (such as X-ray fluorescence, infrared spectroscopy, electron paramagnetic resonance). This will allow us to address several aspects, such as the detection of trace components, the coordination of transition metals, the investigation of ink-paper interactions and the degradation. The spectral measurement datasets of the model samples will serve as a basis for accurate characterisation and classification of objects from the national collections. Experimental analyses will be combined with theoretical research (modelling), and this will serve as a basis for recommendations (guidelines) for the conservation of cultural heritage.

Objectives

The overall objective of the proposed project is to develop analytical methodology for appropriate characterisation and classification inks from Slovenian national collections in as non-invasive a way as possible and to propose optimal conditions for the preservation of such inks and works on paper worldwide. Examples of works (manuscripts, drawings on paper) will be selected from the collections of the National and University Library of Ljubljana and the National Gallery of Ljubljana and researched within the proposed project (DS3). Figure 1 shows an example of a manuscript and a drawing that are candidates for this investigation. In order to achieve this general objective, several specific objectives will need to be met:

OBJECTIVE 1: Optimisation of the SERS process using an HPC-based SERS substrate for minimally invasive or non-invasive characterisation of SERS inks with in situ characterisation capability (DS2)

OBJECTIVE 2: Development of an analytical methodology for good ink characterisation (DS2)

OBJECTIVE 3 Determine the effect of different wavelengths and light intensities on the degradation and stability of inks, and complement the predictive model with developed response functions based on experimental measurements to produce an all-encompassing model of ink degradation (DS4)

OBJECTIVE 4: Preparation of guidelines for the selection of a light source for curators (DS4)

Figure 1: a) manuscript legacy of Jernej Kopitar; b) drawing by Hinko Smrekar; both examples are classified as iron-tan ink (photodocumentation of the National and University Library, Ljubljana)

PROJECT PHASES AND THEIR IMPLEMENTATION

The project work (core postdoctoral project) is divided into 4 work streams (WSS). WSS 1 will be dedicated to project management and dissemination of the results achieved. The main part of the research and development work will be carried out in WP 2, WP 3 and WP 4. Each WP is further subdivided into tasks (N), the interdependence of the WPs is shown in a mind map (Figure 2).

Figure 2: Project information flow (Pert diagram).

DS1 Project management and dissemination (months 1-24)

Task 1.1 Project Advisory Board (months 1-24)

Task 1.2 Dissemination of results in scientific and peer-reviewed journals and conferences (Month 12 - 24)

DS2 Optimisation of the SERS procedure and basis for an analytical methodology for ink characterisation (Months 1-10)

Task 2.1 Development of the SERS process (months 1-8)

Task 2.2 Preparation of model ink samples on paper (months 1 - 8)

Task 2.3 Develop a spectral database of model ink samples (months 8-10)

DS3 Characterisation of inks obtained from national collections - development of a database (months 10-18),

Task 3.1 Selection of works on paper from national collections (10th - 11th month)

Task 3.2 Classification according to elemental composition (months 11-12)

Task 3.3 Molecular characterisation (months 12-17)

Task 3.4 Classification of inks (months 17-18)

DS4 Study of changes in selected inks due to light (months 16-24)

Task 4.1 Select the most common inks and light sources (Month 16-17)

Task 4.2 Studies on the effect of light on the stability of inks (months 17-22)

Task 4.3 Guidelines for the selection of light sources (months 22-24)

BIBLIOGRAPHICAL REFERENCES ARISING DIRECTLY FROM THE IMPLEMENTATION OF THE PROJECT

Original scientific article

RETKO, Klara, LEGAN, Lea, KOSEL, Janez, ROPRET, Polonca. Identification of iron gall inks, logwood inks, and their mixtures using Raman spectroscopy, supplemented by reflection and transmission infrared spectroscopy. Heritage science. 2024, vol. 12, article no. 212, pp. 1-20, illus. ISSN 2050-7445. https://heritagesciencejournal.springeropen.com/articles/10.1186/s40494-024-01323-0, DOI: 10.1186/s40494-024-01323-0. [COBISS.SI-ID 199628035], [JCR, SNIP, WoS, Scopus]

Published abstract of a scientific paper at the conference

RETKO, Klara, LEGAN, Lea, KAVČIČ, Maša, PASNAK, Ekaterina, MALEŠIČ, Jasna, ROPRET, Polonca. Combining different spectroscopic techniques for the investigation of inks : from mock-ups to historical samples. In: ANŽUR, Lana Nastja (ed.), MAHGOUB, Hend (ed.). 1st conference of the Slovenian node of the European Research Infrastructure for Heritage Science : book of abstracts : 22nd November, 2023, University of Ljubljana, Ljubljana, Slovenia. Ljubljana: Faculty of Chemistry and Chemical Technology, 2023. pp. 38-41, illustrated. ISBN 978-961-7078-41-1. https://www.e-rihs.si/uploads/E-RIHS.SI%201st%20Conference%20BoA.pdf. [COBISS.SI-ID 177175043]

RETKO, Klara, LEGAN, Lea, KAVČIČ, Maša, ROPRET, Polonca. Complementary characterisation of different inks by Raman, FTIR over XRF spectroscopy. In.: ROUSAKI, Anastasia (ur.), KOULOUMPI, Eleni (ur.), VERMEERSCH, Eva (ur.). 11th International Conference on the Application of Raman Spectroscopy in Art and Archaeology (RAA2023) : book of abstracts : 4-5 September 2023, Raman spectroscopy training school : 6-9 September 2023, RAA2023 Conference. Athens: National Gallery-Alexandros Soutsos Museum, 2023. Pp. 129, illus. [COBISS.SI-ID 164153859]

RETKO, Klara, EBEID, Hassan, MORENO CASTAÑO, Sara, STRLIČ, Matija, ROPRET, Polonca. Surface enhanced Raman spectroscopy of natural dyes in historical Islamic paper. In: ROUSAKI, Anastasia (ed.), KOULOUMPI, Eleni (ed.), VERMEERSCH, Eva (ed.). 11th International Conference on the Application of Raman Spectroscopy in Art and Archaeology (RAA2023) : book of abstracts : 4-5 September 2023, Raman spectroscopy training school : 6-9 September 2023, RAA2023 Conference. Athens: National Gallery-Alexandros Soutsos Museum, 2023. Pp. 35, illus. [COBISS.SI-ID 164165123]

RETKO, Klara, EBEID, Hassan, STRLIČ, Matija, ROPRET, Polonca, ELNAGGAR, Abdelrazek. Insights into the non-invasive characterisation of dye-containing iron-gall inks by Raman spectroscopy. In. Slovenian Chemical Days 2023 = 29th Annual Meeting of the Slovenian Chemical Society : book of abstracts : 13.-15. september 2023, Portorož, Portorose, Slovenia. Ljubljana: Slovenian Chemical Society, 2023. pp. 129. ISBN 978-961-95922-2-9. [COBISS.SI-ID 191675907]

RETKO, Klara, LEGAN, Lea, KNAFLIČ, Tilen, HUŠ, Matej, ROPRET, Polonca. Spectroscopic analysis of mixtures of iron gall inks and logwood. In: ZISI, Angeliki (ed.), DE FERRI, Lavinia (ed.). InART : book of abstracts : 6th International Conference on Innovation in Art Research and Technology : 4-7 June 2024, Oslo, Norway. Oxford: Archaeopress Archaeology, 2024. pp. 204-205. ISBN 978-1-80327-742-4. [COBISS.SI-ID 199219203]

RETKO, Klara, LEGAN, Lea, KRAŠEVEC, Ida, ROPRET, Polonca. Impact of light, temperature and relative humidity on iron gall inks, logwood inks, and their mixtures on paper. In: PINTAR, Albin (ed.). Slovenski kemijski dnevi 2024 : zbornik sumetkov = book of abstracts : 30 let = 30 years : 18.-20. september 2024, Bernardin, Portorož. Electronic ed. Ljubljana: Slovene Chemical Society, 2024. p. 122. ISBN 978-961-95922-3-6. https://skd2024.chem-soc.si/wp-content/uploads/2024/08/SKD-2024-Zbornik-povzetkov_compressed.pdf. [COBISS.SI-ID 208553731]

Published abstract of an expert contribution at the conference

RETKO, Klara, LEGAN, Lea, KAVČIČ, Maša, MALEŠIČ, Jasna, ROPRET, Polonca. Inks and ink speciation by spectroscopic techniques. Conservator-restaurateur : abstracts of a professional meeting. 2024, pp. 107, 152, illus. ISSN 1854-5289. [COBISS.SI-ID 197809155]

Final report on the results of the surveys

RETKO, Klara, NIKOLIĆ, Nik. Investigation of selected ink samples on paper of the UL FKKT collection by Raman microscopy : report of heritage research within the ARIS Z1- 4404 project "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2024. 34 p., illus. [COBISS.SI-ID 187425795]

RETKO, Klara, NIKOLIĆ, Nik. Characterisation of selected ink samples on paper from the UL FKKT collection : report of heritage research within the ARRS (ARIS) project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 38 p., illus. [COBISS.SI-ID 181306371]

RETKO, Klara, NIKOLIĆ, Nik, SEMENIČ, Dona. Colorimetry of selected ink samples on paper : report of heritage research within the ARRS project Z1-4404 "Characterization and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 60 p., illus. [COBISS.SI-ID 163580419]

RETKO, Klara. Investigation of selected artificially aged ink samples on paper (P1) by Raman spectroscopy - comparison of thermal and light ageing : heritage research report. Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 99 p., illus. [COBISS.SI-ID 171937539]

RETKO, Klara. Preparation of samples of selected inks on paper within the ARRS project Z1-4404 (Characterization and stability of inks on paper) : report of heritage research within the ARRS project Z1-4404 "Characterization and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 79 p., illus. [COBISS.SI-ID 153851395]

RETKO, Klara. Spectral database of FT- Raman spectra of selected inks - part 3 : report of heritage research within the ARRS project Z1- 4404 "Characterization and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 45 p., illus. [COBISS.SI-ID 163583491]

RETKO, Klara. Spectral database of Raman spectra of selected inks - part 1 : report of heritage research within the ARRS project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 83 p., illus. [COBISS.SI-ID 158655747]

RETKO, Klara, NIKOLIĆ, Nik. Spectral database of Raman spectra of selected inks - part 2 : report of heritage research - comparison of spectra of liquid and dried inks within the ARRS project Z1- 4404 "Characterization and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 66 p., illus. [COBISS.SI-ID 163582211]

RETKO, Klara, OCEPEK, Jan. Spectral database of Raman spectra of selected inks - Part 4 : report of heritage research - comparison of Raman spectra (785, 532 nm) of selected liquid and dried inks. Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 121 p., illus. [COBISS.SI-ID 168638979]

RETKO, Klara, NIKOLIĆ, Nik. Spectral database of Raman spectra of selected inks - part 5 : report of heritage research - comparison of spectra of paper, ink and ink on paper (PAPIR 1). Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 46 p., illus. [COBISS.SI-ID 171935491]

RETKO, Klara. Spectral database of FTIR reflectance spectra of selected inks on P5 paper : report of heritage research within the ARRS project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 62 p., illus. [COBISS.SI-ID 163584515]

LEGAN, Lea. Spectral database of FTIR reflectance spectra of selected inks on P1 paper : report of heritage research within the ARRS project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 62 p., illus. [COBISS.SI-ID 163600643]

LEGAN, Lea. Spectral database of FTIR reflectance spectra of selected inks on P1, TRH ageing paper : report of heritage research within the ARRS project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 67 p., illus. [COBISS.SI-ID 163603203]

LEGAN, Lea. Spectral database of FTIR reflectance spectra of selected inks on paper with P1, UV - Vis ageing : report of heritage research within the ARRS project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 109 p., illus. [COBISS.SI-ID 163603971]

LEGAN, Lea. Spectral database of FTIR reflectance spectra of selected inks on P5, TRH ageing paper : report of heritage research within the ARRS project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 68 p., illus. [COBISS.SI-ID 163609091]

RETKO, Klara, OCEPEK, Jan. Surface-enhanced Raman spectroscopy for the determination of selected inks on paper : report of legacy research within the ARRS (ARIS) project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 39 p., illustrated [COBISS.SI-ID 181310723]

RETKO, Klara, SEMENIČ, Dona. Comparison of spectra (portable Raman spectrometer) of inks on different papers; influence of T, RH : report of legacy research within the ARRS project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 139 p., illustrated [COBISS.SI-ID 187038211]

RETKO, Klara, NIKOLIĆ, Nik. Spectral database of Raman spectra of selected inks - portable Raman spectrometer (additional samples) : report of the legacy research within the ARRS project Z1- 4404 "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2023. 46 p., illustrated [COBISS.SI-ID 181211907]

RETKO, Klara, KRAŠEVEC, Ida. Analysis (colorimetry and microbleaching) of selected inks on paper exposed to light ageing (LED) : report of heritage research within the ARIS Z1-4404 project "Characterisation and stability of inks on paper". Ljubljana: Institute for the Protection of Cultural Heritage of Slovenia, Centre for Conservation, Research Institute, 2024. 48 p., illus. [COBISS.SI-ID 207188995]

COMPOSITION OF THE PROJECT TEAM WITH LINKS TO SICRIS DATA

(/:Postdoctoral basic research project)

Project leader: Klara Retko, code: 35834, link to SICRIS: https://cris.cobiss.net/ecris/si/sl/researcher/41005

BASIC INFORMATION ON FINANCING

The project is (co-)funded by ARRS with 1700 annual B-grade hours for a period of 2 years. The (co)financing will start on 1 October 2022.