Characterization of writing materials of books of great historical-artistic value by FT-IR and micro-raman spectroscopy

Vito Librando, Zelica Minniti

Abstract


Summary

This work describes the application of Fourier-Transform Infrared and Raman spectroscopic techniques for the characterization of cellulose paper samples and inks used on ancient writing materials. These samples from books of high historical and artistic interest were provided by the Public Library of Syracuse.

The ancient paper showed a characteristic pattern of carbonyl groups, whose vibration modes were observed in FTIR spectra. The spectra of ancient paper samples were compared to each other and to modern paper in order to highlight differences in conservation state between new and old papers. The paper aging process is related to the presence of acid substances and oxidative agents that result in cellulose hydrolysis leading to the shortening of its chain along with changes in the amount of the crystalline form. This hydrolysis causes changes in hydrogen bonds and consequently change the CCH, COH, OCH and HCH bending vibrations mode. In this work, the FTIR and Raman spectra of inks used on ancient paper and parchment samples were also discussed.

 

Riassunto

Questo lavoro descrive l’applicazione delle tecniche spettroscopiche infrarosse in trasformata di Fourier e Raman per la caratterizzazione di campioni di carta di cellulosa e inchiostri utilizzati su antichi materiali scrittori. Questi campioni provenienti da libri di notevole interesse storico e artistico sono stati forniti dalla Biblioteca Comunale di Siracusa.
La carta antica ha mostrato un modello caratteristico di gruppi carbonilici, le cui modalità di vibrazione sono state osservate in spettri FTIR. Gli spettri dei campioni di carta antica sono stati confrontati tra loro e con quelli della carta moderna al fine di evidenziare le differenze tra lo stato di conservazione della carta nuova e vecchia. Il processo di invecchiamento della carta è legato alla presenza di sostanze acide e agenti ossidanti che provocano l’idrolisi di cellulosa che porta all’accorciamento della sua catena con cambiamenti nella
quantità della forma cristallina. Questa idrolisi provoca cambiamenti nei legami a idrogeno che influenzano i modi vibrazioni di bending di CCH, COH, OCH e HCH.
In questo lavoro sono stati anche discussi gli spettri FTIR e Raman di inchiostri usati su campioni di carta e pergamena antica.

 

Résumé

Ce travail décrit l’application des techniques de spectroscopie infrarouge à transformée de Fourier et Raman pour la caractérisation d’échantillons de papier cellulose et d’encre qui ont été utilisés dans des manuscrits anciens. Ces échantillons proviennent de livres d’un très grand intérêt historique et artistique, qui nous ont été fournis par la bibliothèque de Syracuse (Biblioteca Comunale di Siracusa).
Le papier ancien présentait un modèle caractéristique de groupes carbonyles, dont les modalités vibratoires ont été observées dans des spectres FTIR. Les spectres des échantillons de papier ancien ont été comparés entre eux et avec ceux du papier moderne, afin de faire ressortir les différences entre l’état de conservation du papier ancien et nouveau. Le processus de vieillissement du papier est lié à la présence de substances acides et d’agents oxydants qui provoquent l’hydrolyse de la cellulose et par conséquent le raccourcissement de sa chaîne et des changements dans la quantité de cellulose cristalline. Cette hydrolyse provoque des changements dans les liaisons hydrogène qui
à leur tour influencent les modes vibratoires de bending de CCH, COH, OCH et HCH.
Ce travail discute également des spectres FTIR et Raman des encres utilisés sur
des échantillons de papier et de papier parchemin ancien.

 

Zusammenfassung

Dieses Werk beschreibt die Anwendung der Fourier-Transform-Ramanspektroskopie zur Charakterisierung von Zellulosepapierproben und auf antiken Schriftstücken verwendeten Tinten. Diese aus Büchern von beachtlichem historischem und künstlerischem Interesse stammenden Proben wurden von der Stadtbibliothek von Syrakus zur Verfügung gestellt.
Das antike Papier zeigte ein charakteristisches Modell von Carbonylgruppen, deren Schwingungsverhalten in FT-IR-Spektren beobachtet wurde. Die Spektren der antiken Papierproben wurden untereinander und mit Proben modernen Papiers verglichen, um die Unterschiede zwischen den Konservierungszuständen neuen und alten Papiers festzustellen.
Der Alterungsprozess von Papier ist mit dem Vorhandensein saurer Stoffe und
Oxydantien verbunden, die eine Hydrolyse der Zellulose und somit die Verkürzung ihrer Molekülkette hervorrufen, so dass mengenmäßige Veränderungen der Kristallform eintreten.
Diese Hydrolyse bewirkt Veränderungen in den Bindungen mit dem Wasserstoff, welche das Bending - Schwingungsverhalten von CCH, COH, OCH und HCH beeinflussen.
In diesem Werk werden auch die FTIR- und Raman-Spektren der Tinten besprochen, die auf antiken Papier- und Pergamentproben verwendet wurden.

 

Resumen

Este trabajo describe la aplicación de técnicas de espectroscopía de infrarrojo con transformada de Fourier y Raman para caracterizar muestras de papel de celulosa y tintas empleadas sobre antiguos materiales de escritura. Dichas muestras, provenientes de libros de destacado interés histórico y artístico, han sido proporcionadas por la Biblioteca Municipal de Siracusa.
El papel antiguo ha mostrado un modelo característico de los grupos carbonilos,
cuyas modalidades de vibración se han observado en espectros FTIR. Los espectros de las muestras de papel antiguo se han comparado entre sí y con los del papel moderno para evidenciar las diferencias entre el estado de conservación del papel nuevo y el viejo. El proceso de envejecimiento del papel está relacionado con la existencia de sustancias ácidas y agentes oxidantes que provocan la hidrólisis de la celulosa. Este fenómeno comporta el acortamiento de la cadena, con modificaciones en la cantidad de la forma cristalina, y provoca cambios en los enlaces de hidrógeno que influyen en
los modos de las vibraciones de deformación de CCH, COH, OCH y HCH.
En este trabajo, asimismo, se acomete una discusión sobre los espectros FTIR y
Raman de tintas empleadas sobre muestras de papel y pergamino antiguo.

 

简介

本文介绍了傅里叶变换红外光谱和拉曼光谱技术的应用:检测纤维纸张样品,以及古
代书写材料上墨水样本的特性。这些样品均取自具有极高历史和艺术价值的书籍,书
籍由Siracusa (锡拉库萨市) 政图书馆提供。
根据FTIR光谱测定观察得到的震动方式显示,古代纸张中具有碳基结构特性。古代
纸张样本的光谱相互比较后,还与现代纸张光谱进行了比较,以得出新旧纸张保存状
态的差异。纸张的老化过程与其中酸性物质和氧化剂相关,这些物质促成纤维素的水
解,进而使碳链缩短、晶体结构数量变化。这些水解反应造成氢键连接方式的变化,
进而影响CCH,COH,OCH和HCH弯曲振动的模式。
此外在这项测试中,同样还进行了样本纸张和羊皮纸上墨水FTIR和拉曼光谱的分
析。

 

Резюме

Объектом этой работы является применение методов ИК рамановской спек-
троскопии с Фурье-преобразованием для определения характеристик образцов целлюлозной бумаги и чернил, использованных в старинных материалах для письма. Данные образцы, полученные из книг, представляющих значительную историческую и художественную ценность, были предоставлены городской би-блиотекой г. Сиракуза.
В старинной бумаге была обнаружена характерная модель карбонильных
групп, способы колебания которых были изучены в ИК-спектрах с Фурье-преобра-зованием. Для выявления разницы между состоянием хранения новой и старой бумаги спектры образцов старинной бумаги были сопоставлены друг с другом и со спектрами, полученными от современной бумаги. Процесс старения бумаги связан с наличием кислотных веществ и окисляющих агентов, вызывающих ги-дролиз целлюлозы. Это приводит к сокращению ее цепи и к количественным из-менениям кристаллической формы. Гидролиз вызывает изменение водородных связей, оказывающих влияние на изгибное колебание CCH, COH, OCH и HCH.
В данной работе также изучены ИК-спектры с Фурье-преобразованием и Ра-
ман-спектры чернил, используемых на образцах старинной бумаги и пергамента


Keywords


spectroscopy; infrared; Raman; cellulose; ink

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DOI: 10.6092/issn.1973-9494/4740

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