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Proceedings e report - Firenze University Press

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NIR ARCHAEOMETRY FOR ARCHAEOLOGICAL WOOD - OBSERVATION USING DEUTERIUM EXCHANGE<br />

where A t (OH) and A t=0 (OH) are the integrated absorbances of the OH-related band measured at<br />

saturated diffusion condition and before the start of the deuteration, respectively. The isolated left<br />

wing -7000 cm -1 , and the integrated absorbance of ±20 cm -1 at 6718, 6600, 6450, and 6287 cm -1 were<br />

employed for the calculation of the accessibilities of the Am, Sc, CI, CII and CIII regions, respectively.<br />

Absorbance<br />

1.5<br />

1.0<br />

0.5<br />

0<br />

-0.5<br />

10000<br />

Before deuteration,<br />

thermal treatment time 0hour<br />

After deuteration,<br />

thermal treatment time 0hour<br />

8000 6000<br />

Wavenumber (cm<br />

4000<br />

-1 )<br />

Wavenumber (cm-1 0<br />

7000<br />

6500<br />

)<br />

(a) (b)<br />

198<br />

Absorbance<br />

0.3<br />

0.2<br />

0.1<br />

A m Sc<br />

C I<br />

A m: >6950 cm -1<br />

S c : 6718±20 cm -1<br />

C I : 6600±20 cm -1<br />

C II: 6450±20 cm -1<br />

C III:6287±20 cm -1<br />

Fig. 2; The variation of (a) NIR original spectra and (b) baseline corredted NIR spectra (7200-6000cm -1 ) with<br />

deuterium exchange.<br />

3.3. Variation of accessibility at OH-related absorption with thermal treatment time<br />

Thermal changes of the saturation accessibilities in thermally-treated wood samples were observed.<br />

During the initial stage of hydrothermal treatment up to tht = 10 hr, the saturation accessibilities of Am<br />

(i.e. the amorphous region) rapidly increased with increment of tht. The increases of the saturation<br />

accessibility suggest that the inter-microfibril space has expanded causing disintegration in wood cell<br />

wall, and that, consequently, the region itself disappears locally. In the case of Sc originating from the<br />

semi-crystalline regions, the saturation accessibility for D2O also increased. Also in the cases of CI, CII<br />

and CIII, the saturation accessibilities for D2O increased. From the observation of variation of<br />

accessibility with the thermal treatment time, respectively, we could find the supermolecular<br />

difference of the fine structure in the microfibrils in the cell walls.<br />

Accessibility<br />

100<br />

80<br />

60<br />

40<br />

20<br />

0<br />

Am Sc CI CII CII I<br />

0 20 40 60 80 100 120 140 160<br />

Thermal treatment time (hour)<br />

C II<br />

C III<br />

6000<br />

Fig. 3- The variation of accessibility of amorphous<br />

(Am), semi-crystalline (Sc), crystalline regions (CI, CII,<br />

CIII) in cellulose with thermal treatment time.<br />

Acknowledgement<br />

This study was partly supported by Research Fellowship for Young Scientist from the Japan Society<br />

for the Promotion of Science (grant numbers 20007231).<br />

References<br />

1. S. Tsuchikawa (2007): A Review of Recent Near Infrared Research for Wood and Paper. Appl.<br />

Spectrosc. Rev. 42: 43-71.<br />

2. S. Tsuchikawa, H. Yonenobu and H. W. Siesler (2005): Near-infrared spectroscopic observation<br />

of the ageing process in archaeological wood using a deuterium exchange method The Analyst,<br />

130: 379-384.

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