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      Monitoring Wood Degradation during Weathering by Cellulose Crystallinity

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          Abstract

          The degree of crystallinity of cellulose was used for assessing the degradation level of coated and uncoated samples of pine wood after weathering. X-ray diffraction (XRD) and Fourier Transform Infrared (FT-IR) spectroscopy measured the changes in the surface crystallinity of cellulose resulting from weathering, both natural and artificial. Both techniques revealed an increase in the crystallinity index (CI) of cellulose when wood was subjected to weathering. An increase in the size of crystallites was also observed by XRD measurements. These results were related to the reduction of the amorphous fractions of wood, and, consequently, to the enrichment of the relative crystalline content. Thanks to FT-IR analysis, the degradation of hemicellulose was observed for uncoated samples after exposure to artificial weathering. The effect of weathering was less evident on coated samples because of the protective action of the coating. A good correlation between the crystallinity indexes obtained from FT-IR and XRD was found. The experimental results proved that the proposed method may be a very useful tool for a rapid and accurate estimation of the degradation level of wood exposed to weathering. This methodology can find application in the field of conservation and restoration of wooden objects or in the industry of wood coatings.

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          Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance

          Although measurements of crystallinity index (CI) have a long history, it has been found that CI varies significantly depending on the choice of measurement method. In this study, four different techniques incorporating X-ray diffraction and solid-state 13C nuclear magnetic resonance (NMR) were compared using eight different cellulose preparations. We found that the simplest method, which is also the most widely used, and which involves measurement of just two heights in the X-ray diffractogram, produced significantly higher crystallinity values than did the other methods. Data in the literature for the cellulose preparation used (Avicel PH-101) support this observation. We believe that the alternative X-ray diffraction (XRD) and NMR methods presented here, which consider the contributions from amorphous and crystalline cellulose to the entire XRD and NMR spectra, provide a more accurate measure of the crystallinity of cellulose. Although celluloses having a high amorphous content are usually more easily digested by enzymes, it is unclear, based on studies published in the literature, whether CI actually provides a clear indication of the digestibility of a cellulose sample. Cellulose accessibility should be affected by crystallinity, but is also likely to be affected by several other parameters, such as lignin/hemicellulose contents and distribution, porosity, and particle size. Given the methodological dependency of cellulose CI values and the complex nature of cellulase interactions with amorphous and crystalline celluloses, we caution against trying to correlate relatively small changes in CI with changes in cellulose digestibility. In addition, the prediction of cellulase performance based on low levels of cellulose conversion may not include sufficient digestion of the crystalline component to be meaningful.
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            Structural analysis of photodegraded wood by means of FTIR spectroscopy

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              Effects of modified cellulose nanocrystals on the barrier and migration properties of PLA nano-biocomposites.

              The aim of this paper is to report the impact of the addition of cellulose nanocrystals on the barrier properties and on the migration behaviour of poly(lactic acid), PLA, based nano-biocomposites prepared by the solvent casting method. Their microstructure, crystallinity, barrier and overall migration properties were investigated. Pristine (CNC) and surfactant-modified cellulose nanocrystals (s-CNC) were used, and the effect of the cellulose modification and content in the nano-biocomposites was investigated. The presence of surfactant on the nanocrystal surface favours the dispersion of CNC in the PLA matrix. Electron microscopy analysis shows the good dispersion of s-CNC in the nanoscale with well-defined single crystals indicating that the surfactant allowed a better interaction between the cellulose structures and the PLA matrix. Reductions of 34% in water permeability were obtained for the cast films containing 1 wt.% of s-CNC while good oxygen barrier properties were detected for nano-biocomposites with both 1 wt.% and 5 wt.% of modified and un-modified cellulose nanocrystals, underlining the improvement provided by cellulose on the PLA films. Moreover, the migration level of the studied nano-biocomposites was below the overall migration limits required by the current normative for food packaging materials in both non-polar and polar simulants. Copyright © 2012 Elsevier Ltd. All rights reserved.
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                Author and article information

                Journal
                Materials (Basel)
                Materials (Basel)
                materials
                Materials
                MDPI
                1996-1944
                19 October 2012
                October 2012
                : 5
                : 10
                : 1910-1922
                Affiliations
                Department of Engineering for Innovation, University of Salento, via Monteroni, Lecce 73100, Italy; E-Mails: roberta.delsole@ 123456unisalento.it (R.D.S.); donato.cannoletta@ 123456unisalento.it (D.C.); giuseppe.vasapollo@ 123456unisalento.it (G.V.); alfonso.maffezzoli@ 123456unisalento.it (A.M.)
                Author notes
                [* ]Author to whom correspondence should be addressed; E-Mail: francesca.lionetto@ 123456unisalento.it ; Tel.: +39-083-229-7326; Fax: +39-083-229-7254.
                Article
                materials-05-01910
                10.3390/ma5101910
                5449036
                5bd03d42-b727-4be2-b6c1-89e2f8f2c31f
                © 2012 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license ( http://creativecommons.org/licenses/by/3.0/).

                History
                : 10 September 2012
                : 11 October 2012
                : 17 October 2012
                Categories
                Article

                crystallinity,pine wood,x-ray diffraction (xrd),fourier transform infrared (ft-ir),outdoor weathering,wood coatings,lignin,cellulose,wood degradation

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