There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Wood heat treatment has increased significantly in the last few years and is still growing as an industrial process to improve some wood properties. The first studies on heat treatment investigated mainly equilibrium moisture, dimensional stability, durability and mechanical properties. Mass loss, wettability, wood color, and chemical transformations have been subsequently extensively studied, while recent works focus on quality control, modeling, and study the reasons for the improvements. This review explains the recent interest on the heat treatment of wood and synthesizes the major publications on this subject on wood properties, chemical changes, wood uses, and quality control.

https://bioresources.cnr.ncsu.edu/BioRes_04/BioRes_04_1_0370_Esteves_P_Wood_Mod_Heat_Treatment_Rev_367.pdf

Wood modification by heat treatment: a review.

Characterisation of thermally modified hard- and softwoods by 13C CPMAS NMR

Confocal Raman microscopy was used to illustrate changes of molecular composition in secondary plant cell wall tissues of poplar (Populus nigra × Populus deltoids) wood. Two-dimensional spectral maps were acquired and chemical images calculated by integrating the intensity of characteristic spectral bands. This enabled direct visualization of the spatial variation of the lignin content without any chemical treatment or staining of the cell wall. A small (0.5 μm) lignified border toward the lumen was observed in the gelatinous layer of poplar tension wood. The variable orientation of the cellulose was also characterized, leading to visualization of the S1 layer with dimensions smaller than 0.5 μm. Scanning Raman microscopy was thus shown to be a powerful, nondestructive tool for imaging changes in molecular cell wall organization with high spatial resolution.

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Chemical Imaging of Poplar Wood Cell Walls by Confocal Raman Microscopy

Thermal treatments of beech wood with different temperature loads on the wood cause characteristic changes in the chemical composition. The determination of specific changes was carried out by means of suitable methods, both wet chemical and instrumental analyses. It could be confirmed that in addition to the degradation of polyoses, lignin, known as the thermally most stable compound, shows significant thermal alterations too.

Chemical changes during the production of thermo-treated beech wood

Scots pine planks were heat‐treated under steam in a temperature range of 100–240°C at every 20°C. Changes in chemical structure of the wood samples were examined with UV resonance Raman (UVRR) and Fourier transform infrared (FT‐IR) spectroscopies. Prior to the FT‐IR and UVRR analysis, the heartwood part of wood samples were ground and extracted with acetone. Both the extracts and the extracted samples were analyzed. In addition, Klason lignin contents of the samples were determined. The FT‐IR and UVRR spectroscopy were powerful techniques to monitor chemical changes in the heat‐treated wood samples. Results confirmed most of what determined previously by other research groups using different techniques. The UVRR and FT‐IR spectra of acetone extracts showed that lignin became partly acetone soluble after a heat treatment of 180°C or greater. Increased levels of free phenolic hydroxyl groups were detected in lignin, probably due to cleavages of β‐O‐aryl ether interunit linkages. The amount of extr...

Thermal Modifications in Softwood Studied by FT‐IR and UV Resonance Raman Spectroscopies

Scots pine battens were heat-treated at 100–240o C under saturated steam. Cross-sections of heat-treated battens were analysed using ATR and reflection FTIR microscopies. A typical absorption band of fats and waxes at 1740 cm-1 was detected on the sapwood edges in the temperature range of 100–160o C, indicating that fats and waxes moved along the axial parenchyma cells to the surface of the sapwood during the heat treatment. At the elevated temperatures (above 180° C) fats and waxes disappeared from the sapwood surface and were no longer detected with FTIR spectroscopy. Resin acids were detected at temperatures between 100 and 180o C in the middle of the battens. IR spectra of these spots showed a characteristic absorption band of resin acids at 1697 cm-1. At 200o C resin acids were not detected in the middle of the battens; however, resin acids were detected at distances of 500 and 600 mm from the midpoint of the battens and on the edges of battens. At temperatures above 200° C, resin acids had disappeared from the wood.

The effects of a heat treatment on the behaviour of extractives in softwood studied by FTIR spectroscopic methods

Scots pine samples, heat-treated (225°C under steam) and reference (kiln-dried), were exposed to natural weathering for 7 years in Espoo, Finland. The weathered and unweathered samples were examined with FTIR, UV resonance Raman, and 13C CPMAS NMR spectroscopies. The spectroscopic results revealed that the lignin contents of the weathered heat-treated and especially of the weathered reference softwood samples diminished significantly. The surface of the weathered heat-treated sample was still rich in aromatic and conjugated carbonyl structures, whereas the surface of the reference sample was enriched with cellulose. These results indicated that weathering products of lignin were leached out with water from the reference sample, whereas in the heat-treated wood they were largely unleachable. The structure of the heat-treated wood was modified and degradation products did not leach out as easily as in the case of the reference sample. The weathering also resulted in a decreased content of amorphous polysaccharides of the reference sample, whereas the changes in the polysaccharide contents between weathered and unweathered heat-treated samples were not as dramatic because the amorphous carbohydrates were already degraded in the heat treatment. The results indicated that heat-treated wood is more resistant to natural weathering than untreated wood. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2128–2134, 2004

Heat‐treated softwood exposed to weathering

Raman spectroscopy of wood and lignin samples is preferably carried out in the near-infrared region because lignin produces an intense laser-induced fluorescence background at visible excitation wavelengths. However, excitation of aromatic and conjugated lignin structures with deep ultra violet (UV) light gives resonance-enhanced Raman signals while the overlapping fluorescence is eliminated. In this study, ultra violet resonance Raman (UVRR) spectroscopy was used to define characteristic vibration bands of model compounds of p-hydroxyphenyl, guaiacyl, and syringyl lignin structures at three excitation wavelengths (229, 244, and 257 nm). The intensities of each band, relative to the intensity of the aromatic vibration band at 1600 cm-1, were defined and the most suitable excitation wavelength was suggested for each structure. p-Hydroxyphenyl structures showed intensive characteristic bands at 1217-1214 and 1179-1167 cm-1 with excitation at 244 nm, whereas the bands of guaiacyl structures were more intensive with 257 nm excitation. Most intensive characteristic bands of guaiacyl structures were found at 1289-1279, 1187-1185, 1158-1155, and 791-704 cm-1. Syringyl structures had almost identical spectra with 244 and 257 nm excitations with characteristic bands at 1514-1506, 1333-1330, and 981-962 cm-1. The characteristic bands of the three structural units were also found from the compression wood, softwood, and hardwood samples, indicating that UVRR spectroscopy can be applied for the determination of chemical structures of lignin.

Ultra Violet Resonance Raman Spectroscopy in Lignin Analysis: Determination of Characteristic Vibrations of p-Hydroxyphenyl, Guaiacyl, and Syringyl Lignin Structures

Mari Nuopponen

Papers

Thermal Modifications in Softwood Studied by FT‐IR and UV Resonance Raman Spectroscopies

The effects of a heat treatment on the behaviour of extractives in softwood studied by FTIR spectroscopic methods

Heat‐treated softwood exposed to weathering

Ultra Violet Resonance Raman Spectroscopy in Lignin Analysis: Determination of Characteristic Vibrations of p-Hydroxyphenyl, Guaiacyl, and Syringyl Lignin Structures

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds of Scots pine (Pinus sylvestris) wood Part I: Lipophilic compounds