Crystallinity fitting using cellulose crystallite models

Cellulose is the most abundant biopolymer on Earth and hence it has enormous potential as a source of renewable energy. The nanoscale properties of cellulose are also import for the wood and papermaking industries. The atomic level structure of naturally occurring cellulose Iβ allomorph is well known [1] and this atomistic model is employed in this study for the cellulose unit cell structure. The cellulose crystallinity cannot be measured directly with scattering methods, but the crystallinity of the sample can be estimated by fitting models of crystalline and amorphous contributions to the sample intensity profile. The crystallinity fitting can be enhanced by improving the cellulose fitting model or the amorphous model. We focus on the cellulose crystallite model. The nanoscale level organization of crystalline cellulose in different plant materials is less well established that the unit cell structure of cellulose Iβ. Information on the texture of the sample is obtained efficiently by measuring the sample with a two-dimensional detector. The two-dimensional diffraction pattern can be used to obtain a wealth of information in one measurement, including the crystallite size, crystallite orientation and the crystallinity of the sample. The small size of cellulose crystallites in the wood cell wall limits the information obtainable from the diffraction pattern as the diffraction peaks widen and overlap. The overlapping of certain diffraction peaks can be studied at least qualitatively by computing the diffraction patterns from crystallite models of varying dimensions. Different models for cellulose crystallite have been suggested in the literature, such as the 36 chain model [2]. We investigate how the crystallinity fitting is influenced by the selected cellulose crystallite model and evaluate the suitability of different models to experimental X-ray scattering data of plant material, wood and highly crystalline cellulose.

Evaluating growth strain of Eucalyptus globulus Labill. from SilviScan measurements

Longitudinal surface strain was measured or estimated using three different methods along the stems of nine trees of 10-year-old Eucalyptus globulus Labill. Wood samples were collected close to the location where the strain was measured or estimated. Microfibril angle (MFA), cellulose crystallite width (Wcryst), microdensity and Young's modulus along the grain (EL) were determined using the SilviScan-2 technology at high spatial resolution. Relationships of measured strain and estimated strain to wood properties were established. The quality of the relationships depends on a particular wood property. Strain was more closely related to mean Wcryst than to any other wood properties. Its relationship with MFA was the next closest. Based on the results of regression analysis, we propose that Wcryst may be suitable for the prediction of surface strain at a moderate level of reliability. Adding measurement of MFA, microdensity and EL does not significantly improve the prediction quality. The strain measurement method also affects the results. The best relationships were obtained with longitudinal displacement measured by the CIRAD method. Strain measured by the strain gauge method gave weak relationships, possibly owing to variation in the cambium age of the specimens.

A Study of Eucalyptus Grandis and Eucalyptus Globulus Branch wood Microstructure

Experimental measurements of cellulose crystallite width and microfibril angle (MFA) by X-ray diffractometry on SilviScan-2 and by conventional microtechniques revealed that the branch wood of the two species exhibited very similar trends in cellulose crystallite width and MFA. Cellulose crystallite width was greater on the upper side of the branches. Tension wood, as defined by the occurrence of gelatinous fibres, was found where cellulose crystallite width was greater than 3.0 nm and 3.1 nm in Eucalyptus grandis and E. globulus respectively. In the tension wood zones, MFA was lower than in the rest of the samples and so could be used to differentiate tension wood. On the lower side of the branches MFA determined from X-ray diffractometry unexpectedly exceeded 40° and fibres were often buckled in both the tangential and radial directions in both species. This local variation in the direction of the fibre axes contributed only slightly to the magnitude of the MFA determined by SilviScan-2. Even given this misalignment, the additional evidence gained from pit angles and cracks in fibre walls suggested that the MFA was indeed around 40° in the lower radius of the branches. This MFA is considerably larger than would be expected for eucalypt stem wood and it is suggested that opposite wood in eucalypt branches may provide a complimentary structural role to that of the tension wood. Experimental measurements of crystallite width produced by SilviScan-2 may be used to accurately locate tension wood zones in both species.

An unusual formation of tension wood in a natural forest Acacia sp.

The determination of microfibril angle (MFA), cellulose crystallite width and microdensity by SilviScan-2 at CSIRO confirmed that several dark bands in the heartwood of an Acacia species were associated with tension wood (TW) fibres. The straight log was taken from a tree of about 30 years of age that had been apparently growing vertically as there were no signs of the usual stimuli for TW formation. The continuous dark bands of about 5 mm width extended radially from the inner heartwood in a spiral pattern and were separated by continuous normal wood bands of similar width. The TW bands continued in the sapwood from the heartwood boundary to the cambium but were not coloured. The dark colour of the TW was probably caused by extractives being polymerised at the heartwood boundary by enzymes in the TW fibres in the sapwood. The MFA and cellulose crystallite width indicated the TW in a band was of similar intensity throughout its length, indicating similar microstructural characteristics at different cambial ages. The initiation of spiral grain formation occurs before that of tension wood in the Acacia samples studied.

THE ASSOCIATION BETWEEN CELLULOSE CRYSTALLITE WIDTH AND TENSION WOOD OCCURRENCE IN EUCALYPTUS GLOBULUS

The association between cellulose crystallite width and the occurrence of tension wood was assessed for Eucalyptus globulus Labill., a commercially important plantation hardwood species. Crystallite width (uncorrected for instrumental broadening) was determined from X-ray diffraction patterns collected on SilviScan-2, an instrument developed for the rapid assessment of wood microstructure. Comparisons of crystallite widths were made using 66 samples of tension wood and normal wood selected randomly from one tree known to have abundant tension wood. Tension wood was found to have significantly wider crystallites than normal wood. The mean crystallite widths were 3.6 nm for tension wood and 3.2 nm for normal wood. The normal wood crystallite widths were consistent with those reported in previous studies, allowing for an experimental broadening equivalent to about 0.5 nm in this work. This study demonstrates that SilviScan-2 is useful for the detection of tension wood in solid wood samples such as increment cores.