Abstract
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.
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References
D. Hunter, Papermaking: History and Technique of an Ancient Craft (Dover, New York, 1987)
H.J. Porck, Rate of Paper Degradation, the Predictive Value of Artificial Aging Tests (European Commission on Preservation and Access, Amsterdam, 2000)
M. Strlič, J. Kolar, Ageing and Stabilisation of Paper (National and University Library, Ljubljana, 2005)
T. Trafela, M. Strlič, J. Kolar, D.A. Lichtblau, M. Anders, D. Pucko, B. Pihlar, Nondestructive analysis and dating of historical paper based on IR spectroscopy and chemometric data evaluation. Anal. Chem. 79, 6319–6323 (2007)
H. Antti, M. Sjöström, L. Wallbäcks, Multivariate calibration models using NIR spectroscopy on pulp and paper industrial applications. J. Chemom. 10, 591–603 (1996)
L. Csefalvayova, M. Strlič, H. Karjalainen, Quantitative NIR chemical imaging in heritage science. Anal. Chem. 83, 5101–5106 (2011)
D. Fengel, M. Ludwig, Possibilities and limits of the FTIR spectroscopy for the characterization of cellulose. Part 1. Comparison of various cellulose fibres and bacteria cellulose. Papier 45, 45–51 (1991)
D. Fengel, Possibilities and limits of the FTIR spectroscopy for the characterization of cellulose. Part 2. Comparison of various pulps. Papier 45, 97–102 (1991)
D. Fengel, Possibilities and limits of the FTIR spectroscopy for the characterization of cellulose. Part 3. Influence of attendant components on Ir-spectrum of cellulose. Papier 46, 7–11 (1992)
D. Fengel, M. Ludwig, M. Przyklenk, Possibilities and limits of the FTIR spectroscopy for the characterization of cellulose. Part 4. Studies on cellulose ethers. Papier 46, 323–328 (1992)
K. Fukunaga, M. Picollo, Terahertz spectroscopy applied to the analysis of artists’ materials. Appl. Phys. A 100, 591–597 (2010)
D.F. Plusquellic, K. Siegrist, E.J. Heilweil, O. Esenturk, Applications of terahertz spectroscopy in biosystems. Chem. Phys. Chem. 8, 2412–2431 (2007)
V.A. Bershtein, V.A. Ryzhov, Far infrared spectroscopy of polymers. Adv. Polym. Sci. 114, 43–121 (1994)
G. Pastorelli, T. Trafela, P. Taday, A. Portieri, D. Lowe, K. Fukunaga, M. Strlič, Characterisation of historic plastics using terahertz time-domain spectroscopy and pulsed imaging. Anal. Bioanal. Chem. 403, 1405–1414 (2012)
B. Ferguson, X.C. Zhang, Materials for terahertz science and technology. Nat. Mater. 1, 26–33 (2002)
M. Tonouchi, Cutting-edge terahertz technology. Nat. Photonics 1, 97–105 (2007)
K. Fukunaga, Y. Ogawa, Application of terahertz spectroscopy for character recognition in a medieval manuscript. IEICE Electron. Express 5(7), 223–228 (2008)
J.M. Manceau, A. Nevin, C. Fotakis, S. Tzortzakis, Terahertz time domain spectroscopy for the analysis of cultural heritage related materials. Appl. Phys. B 90, 365–368 (2008)
Y.S. Lee, Principles of Terahertz Science and Technology (Springer, Berlin, 2009)
I. Hosako, N. Sekine, M. Patrashin, S. Saito, K. Fukunaga, Y. Kasai, P. Baron, T. Seta, J. Mendrok, S. Ochiai, H. Yasuda, At the dawn of a new era in terahertz technology. Proc. IEEE 95, 1611–1623 (2007)
Y. Ueno, K. Ajito, Analytical terahertz spectroscopy. Anal. Sci. 24, 185–192 (2008)
C.J. Strachan, T. Raders, D.A. Newnham, K.C. Gordon, M. Pepper, P.F. Taday, Using terahertz pulsed spectroscopy to study crystallinity of pharmaceutical materials. Chem. Phys. Lett. 390, 20–24 (2004)
S. Wietzke, F. Rutz, C. Jördens, N. Krumbholz, N. Vieweg, C. Jansen, R. Wilk, M. Koch, Applications of Terahertz Spectroscopy in the Plastics Industry. Proc. SPIE, vol. 6840 (2007)
C. Jördens, S. Wietzke, M. Scheller, M. Koch, Investigation of the water absorption in polyamide and wood plastic composite by terahertz time-domain spectroscopy. Polym. Test. 29, 209–215 (2010)
S. Nakajima, H. Hoshina, M. Yamashita, C. Otani, Terahertz imaging diagnostics of cancer tissues with a chemometrics technique. Appl. Phys. Lett. 90, 041102 (2007)
D. Jiang, S. Zhao, J. Shen, Quantitative Analysis of the Mixtures of Illicit Drugs Using Terahertz Time-Domain Spectroscopy. Proc. SPIE, vol. 6840 (2007)
T. Lo, I.S. Gregory, C. Baker, P.F. Taday, W.R. Tribe, M.C. Kemp, The very far-infrared spectra of energetic materials and possible confusion materials using terahertz pulsed spectroscopy. Vib. Spectrosc. 42, 243–248 (2006)
K. Fukunaga, Y. Ogawa, S. Hayashi, I. Hosako, Terahertz spectroscopy for art conservation. IEICE Electron. Express 4, 258–263 (2007)
Terahertz Database: http://www.thzdb.org/. Accessed 22/07/2012
G.R. Brereton, Chemometrics, Data Analysis for the Laboratory and Chemical Plant (Wiley, Sussex, 2003)
SurveNIR project webpage: http://www.science4heritage.org/survenir/. Accessed 22/07/2012
K. Iiyama, A.F.A. Wallis, An improved acetyl bromide procedure for determining lignin in woods and wood pulps. Wood Sci. Technol. 22, 271–280 (1988)
H. Bansa, H.H. Hofer, Die Beschreibung der Benutzbarkeitsqualität gealterter Papiere in Bibliotheken und Archiven. Papier 34, 348–355 (1980)
D. Lichtblau, M. Strlič, T. Trafela, M. Anders, Determination of mechanical properties of historical paper based on NIR spectroscopy and chemometrics—a new instrument. Appl. Phys. A 92, 191–195 (2008)
ASTM International, Standard Practices for Infrared Multivariate Quantitative Analysis vol. E 1655-05 (ASTM International, West Conshohocken, 2005), pp. 356–384
K.H. Esbensen, Multivariate Data Analysis—In Practice, an Introduction to Multivariate Data Analysis and Experimental Design. 5th edn., (2006). CAMO Software AS
Z. Su, B. Yu, P. Han, G. Zhao, C. Gong, Characterization of spectra of lignin from midribs of tobacco at THz frequencies. Front. Optoelectron. China 2, 244–247 (2009)
A.P. Duarte, D. Robert, D. Lachenal, Eucalyptus globulus kraft pulp residual lignins. Part 1. Effects of extraction methods upon lignin structure. Holzforschung 4, 365–372 (2000)
Sigma Aldrich, Material Safety Data sheet: lignin, alkali, product number 471003. http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=GB&language=en&productNumber=471003&brand=ALDRICH. Accessed 22/07/2012
Sigma Aldrich, Material Safety Data sheet: lignin, hydrolytic, product number 371076. http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=GB&language=en&productNumber=371076&brand=ALDRICH. Accessed 22/07/2012
M. Walther, Noncovalent intermolecular forces in polycrystalline and amorphous saccharides in the far infrared. Chem. Phys. 288, 261–268 (2003)
Acknowledgements
This research was financially supported by the Slovenian Research Agency (programme P1-0153) and Ad Futura (Slovene Human Resources and Scholarship Fund). The support of the National Institute of Information and Communications Technology, Japan, is gratefully acknowledged. The authors are grateful for the permission to use the SurveNIR Historic Paper Collection and to Lichtblau e.K. for the use of data on mechanical properties of paper samples from the SurveNIR Collection.
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Trafela, T., Mizuno, M., Fukunaga, K. et al. Quantitative characterisation of historic paper using THz spectroscopy and multivariate data analysis. Appl. Phys. A 111, 83–90 (2013). https://doi.org/10.1007/s00339-012-7525-y
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DOI: https://doi.org/10.1007/s00339-012-7525-y