Elsevier

Microchemical Journal

Volume 91, Issue 2, March 2009, Pages 202-208
Microchemical Journal

Study of 19th century inks from archives in the Palazzo Ducale (Venice, Italy) using various analytical techniques

https://doi.org/10.1016/j.microc.2008.11.002Get rights and content

Abstract

Inks and paper are the main materials and components of library and archive collections. Since the Third century B.C. there has been a continual succession of ink recipes from all over the world, with varying levels of documentation of the recipes used; however, it was only in the 19th century that Europe became the main producer and industrial leader in the discovery of new products. The aim of this study is to find out more about this last historical period, when new inks were created that had never been known or used in the past. In this study we chose four inks: they belong to documents preserved in the archive of the Superintendence Beni architettonici per il paesaggio e per il patrimonio storico artistico ed etnoantropologico (BAPPDAD) of Venice Lagoon, held in the Palazzo Ducale (Ducal Palace) of Venice.

Fourier Transform Infrared Spectroscopy (ATR), Scanning Electron Microscopy (SEM-EDS) and pyrolysis coupled to a gas chromatograph with mass spectrometric detector (Py–GC–MS) allowed us to obtain a qualitative characterization of organic and inorganic elements in three different ink typologies.

Introduction

Usually inks can be described as liquid, semi-liquid or solid preparations, which can be used to draw graphic signs on a support [1]. Recipes have been modified over the ages: the Chinese were the first to use ink, usually mixing lake colours and a black pulverized stone, but the birth of real ink occurred in the Third century B.C. Two centuries later Vitruvius wrote the first true ink recipe in his book De Architectura [2]: he mixed lamp black (a pigment from burnt wood) with camphor and gelatine. Between 2500 and 3000 B.C. a mixture of lamp black ink and oil was used in Egypt while the Arab world only knew of the existence of metal–gall inks. Later Pliny [3] and Cicero described inks based on lamp black, water and Arabic gum. In several Medieval and Renaissance recipe collections the first iron–gall inks were described: for example, in Schedula diversarum artium Theophylus described its stepwise production from vegetable extract maceration to ferrous sulphate addition [4].

It was only since the 17th century that recipes become more precisely written and detailed, and inks that were marketed were produced using more scientific methods. In 1663 Boyle attempted to discover the reaction between vitriol and oak galls; in 1666 Tachen created an ink by mixing oak galls with silver, copper or mercury. In 1748 Lewis defined a product list to obtain a long-lasting ink; and in 1785 Schule synthesized gallic acid, while ten years later Dejeux and Seguin artificially produced tannins. By the 19th century innovative synthetic colorants were employed in ink formulations. In 1856 Leonhardi created alizarin ink, which thanks to its excess of ferrous tannate persists in solution. In order to preserve their metallic pen nibs scientists also studied non acidic inks and in 1830 they found a permanent-light aniline ink: its colour was quite soft so they added some indigo and madder lake to deepen it.

Chemical industrial progress continued and in 1867 nigrosine ink was produced for the first time; in 1873 Coupier and Collin patented induline ink and in 1873 Kwaisser and Hukof produced Methyl Violet. Finally in 1888 governments decided to control the use of these products especially in official documents because of their greater instability [1], [4].

The aging of inks is one of the most important causes of corrosion of paper supports, the mechanism of which depends on the nature of the components and their interactions with the paper. Each ink typology ages differently: the literature pays particular attention to iron–gall inks, which have been shown to be the principal cause of recto-verso penetration. This is due to the acid hydrolysis of cellulose (caused by an excess of sulphuric acid in the recipe) or to iron (II) ion oxidation reactions (caused by an excess of Fe ions) [5], [6]. Conversely carbon black inks are stable thanks to their chemical inertia, they only become duller with age. Whereas synthetic inks do not cause paper corrosion but they are very photosensitive [7].

In this study we have paid particular attention to some documents from a dossier preserved in the archive of the Superintendence BAPPDAD of the Venice Lagoon, held in the Ducal Palace (Palazzo Ducale Venice). They are dated from 1852 to 1888, so they cover a significant time period. The aim of this research is to properly chemically characterize and classify the inks used on these pages to know more about ink and ink products used in the 19th century.

A detailed visual and microscopic observation of the samples was carried out, then each type of ink was analysed to identify all of its constituents: including the pigments, dyestuff and binders. This was done using Attenuated Total Reflection Fourier Transform Infrared spectroscopy (ATR-FT-IR), a non-destructive technique to obtain general information about the organic and inorganic components [8]. Then more specific analyses were carried out to study the individual components, as they may be connected to deterioration processes. Scanning Electron Microscopy (SEM) observations and analyses with microprobe Energy Dispersive X-ray Spectroscopy (EDS) allowed an investigation of the different film morphologies and correlated them to their elemental composition. Results from Pyrolysis–Gas-Chromatography–Mass Spectrometry (Py–GC–MS) enabled the discrimination of iron–gall ink samples from the other sample types.

Section snippets

Samples

For this research we selected representative samples of the three ink typologies found in the dossier, as described before.

Sample 1 (Fig. 1a) is a black printing ink from the headed sheet Regia Prefettura di Venezia, dated 1888. There is no recto-verso penetration visible. Sample 2 (Fig. 1b) is also a black printing ink, but it is from the headed sheet Corpo Reale del Genio Civile di Venezia, dated 1883. Sample 3 (Fig. 1c) is black pen ink from the sheet Regia Prefettura della Provincia di

Conclusions

By the end of this study it was possible to characterize all three ink typologies and distinguish them not only visually but also according to their chemical features.

Printing inks 1 and 2 contain an oleic binder and solid carbon powder, as seen in the FT-IR analyses: this is in agreement with recipes used in the Eighteenth century. The solid phases are different though: ink 2 has an FT-IR peak at 2093 cm 1 that can be related to Prussian Blue, this is supported by the Fe peak in the EDS

Acknowledgements

This work was supported by the National Research Council of Italy (CNR). The authors are grateful to Dr. Roberta Zangrando for technical support and Dr. Annalisa Bristot of the Superintendency BAPPDAD of the Venice Lagoon.

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