Quantitative characterisation of historic paper using THz spectroscopy and multivariate data analysis

THz spectroscopy in the time domain was explored in combination with multivariate data analysis, for quantitative determination of chemical and mechanical properties of historic paper, such as lignin content, tensile strength, and ash content. Using partial least squares (PLS) regression, it was shown that quantitative prediction of the material properties is possible, which indicates the potential of THz spectroscopy for chemical characterisation of complex organic materials of natural origin. In addition, the results demonstrate that THz spectra and PLS loading weights for lignin content differ significantly, which leads to the conclusion that THz spectra of composite macromolecular materials do not represent sums of spectra of the individual components. This supports the premise that THz spectra reflect intermolecular interactions.The study was carried out using 250 historical paper samples from the sixteenth century to present. Although the measurements were performed in vacuum to improve the quality of spectra, THz spectroscopy is in principle non-destructive. This research therefore reinforces the role of THz spectroscopy in characterisation of valuable historic materials, where invasive analysis is often not possible.

[1]  Thomas Rades,et al.  Using terahertz pulsed spectroscopy to study crystallinity of pharmaceutical materials , 2004 .

[2]  Kaori Fukunaga,et al.  Characterisation of historic plastics using terahertz time-domain spectroscopy and pulsed imaging , 2012, Analytical and Bioanalytical Chemistry.

[3]  Henrik Antti,et al.  Multivariate calibration models using NIR spectroscopy on pulp and paper industrial applications , 1996 .

[4]  Iwao Hosako,et al.  Application of terahertz spectroscopy for character recognition in a medieval manuscript , 2008, IEICE Electron. Express.

[5]  Matija Strlič,et al.  Quantitative NIR chemical imaging in heritage science. , 2011, Analytical chemistry.

[6]  M. Koch,et al.  Investigation of the water absorption in polyamide and wood plastic composite by terahertz time-domain spectroscopy , 2010 .

[7]  C. Otani,et al.  Terahertz imaging diagnostics of the cancer tissues with chemometrics technique , 2007, 2006 Joint 31st International Conference on Infrared Millimeter Waves and 14th International Conference on Teraherz Electronics.

[8]  Okan Esenturk,et al.  Applications of terahertz spectroscopy in biosystems. , 2007, Chemphyschem : a European journal of chemical physics and physical chemistry.

[9]  D. Fengel,et al.  Possibilities and limits of the FTIR spectroscopy for the characterization of cellulose. Pt.1: Comparison of various cellulose fibres and bacteria cellulose , 1991 .

[10]  Yun-Shik Lee,et al.  Principles of Terahertz Science and Technology , 2008 .

[11]  Matija Strlič,et al.  Ageing and Stabilisation of Paper , 2005 .

[12]  Costas Fotakis,et al.  Terahertz time domain spectroscopy for the analysis of cultural heritage related materials , 2008 .

[13]  Xicheng Zhang,et al.  Materials for terahertz science and technology , 2002, Nature materials.

[14]  Norihiko Sekine,et al.  At the Dawn of a New Era in Terahertz Technology , 2007, Proceedings of the IEEE.

[15]  H. Bansa,et al.  Die Beschreibung der Benutzbarkeitsqualität gealterter Papiere in Bibliotheken und Archiven , 1980 .

[16]  Henk J. Porck,et al.  Rate of paper degradation : the predictive value of artificial aging tests , 2000 .

[17]  Characterization of spectra of lignin from midribs of tobacco at THz frequencies , 2009 .

[18]  V. A. Ryzhov,et al.  Far infrared spectroscopy of polymers , 1994 .

[19]  Iwao Hosako,et al.  Terahertz spectroscopy for art conservation , 2007, IEICE Electron. Express.

[20]  K. Iiyama,et al.  An improved acetyl bromide procedure for determining lignin in woods and wood pulps , 1988, Wood Science and Technology.

[21]  B. Fischer,et al.  Noncovalent intermolecular forces in polycrystalline and amorphous saccharides in the far infrared , 2003 .

[22]  Yuko Ueno,et al.  Analytical Terahertz Spectroscopy , 2008, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[23]  M. Picollo,et al.  Terahertz spectroscopy applied to the analysis of artists’ materials , 2010 .

[24]  N. Krumbholz,et al.  Applications of terahertz spectroscopy in the plastics industry , 2007, SPIE/COS Photonics Asia.

[25]  Manfred Anders,et al.  Nondestructive analysis and dating of historical paper based on IR spectroscopy and chemometric data evaluation. , 2007, Analytical chemistry.

[26]  Matija Strlič,et al.  Determination of mechanical properties of historical paper based on NIR spectroscopy and chemometrics – a new instrument , 2008 .

[27]  Masayoshi Tonouchi,et al.  Cutting-edge terahertz technology , 2007 .

[28]  Shusen Zhao,et al.  Quantitative analysis of the mixtures of illicit drugs using terahertz time-domain spectroscopy , 2007, SPIE/COS Photonics Asia.

[29]  W. R. Tribe,et al.  The very far-infrared spectra of energetic materials and possible confusion materials using terahertz pulsed spectroscopy , 2006 .

[30]  Richard G. Brereton,et al.  Chemometrics: Data Analysis for the Laboratory and Chemical Plant , 2003 .