Saila Jämsä

Magnetic resonance studies of thermally modified wood

Summary Thermal modification of wood produces a wood material with many interesting properties, such as enhanced dimensional stability, lower equilibrium moisture content and increased biological durability. Changes in the chemical structure of pine (Pinus sylvestris) caused by thermal treatment were investigated by studying various components of wood using 13C CPMAS NMR spectroscopy. Electron spin resonance (ESR) spectroscopy on the same set of samples was used to study the formation and stability of free radicals formed during the treatment. The most remarkable changes revealed by solid state NMR were the increase in relative crystallinity of cellulose and destruction and deacetylation of hemicelluloses. Changes in the lignin fraction were mostly registered as diminishment in the methoxyl content, although the intensity of the aromatic region increased relative to the carbohydrate fraction during the treatment. Increase in the intensities of the ESR signals from thermally treated wood samples proves the formation of stable free radicals. In addition, radical formation is believed to take part in condensation reactions leading to crosslinks within the lignin and possibly between lignin and other wood components. Both of the methods used indicate that the changes are most remarkable when the treatment temperature is over 200°C.

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

Abstract 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 extractable lignin increased with increasing temperature, while the resin in the extracts decreased. UVRR spectra of the wood samples extracted with acetone indicated that the structure of unextractable lignin remained unchanged when heated up to 200°C. Formation of new carbonyl structures was observed in solid wood samples and their extracts. These structures were possibly formed from the degradation products of lignin and hemicelluloses. Lignin content of the samples was increased as a result of degradation of wood hemicelluloses, which started below 200°C.

Long‐term natural weathering of coated ThermoWood

Heat treatment reduces hygroscopicity and accompanying dimensional changes in wood. Prior to coating, pine and spruce boards were heat treated at 225°C for six hours under steam, in order to achieve dimensional stability and durability of wood substrate. The panels were coated surface finishes which are commonly used on exterior cladding, joinery and fences in Finland. Performance of the coated heat‐treated and untreated panels was monitored during five years’ outdoor exposure. Without coating the heat‐treated wood is not weather resistant. The original dark brown colour of the uncoated heat‐treated wood panels was not stable when exposed to weather, turning grey. Cracking of the heat‐treated wood without coating was at the same level as that of the untreated wood despite the lower moisture content of the heat‐treated wood. The unpigmented or low build stains and oils did not prevent cracking of the heat‐treated wood. Weather resistance of the heat‐treated wood was improved by the water‐ or solvent‐borne ...

X-ray scattering studies of thermally modified Scots pine (Pinus sylvestris L.)

Abstract Wood is thermally modified by heating and steaming in order to change its properties, e.g., to improve the biological resistance and to increase the hardness of wood. The structure of thermally modified Scots pine (Pinus sylvestris) was studied using wide-angle, small-angle and ultra-small-angle X-ray scattering methods. Modification temperatures varied from 100 to 240°C. No marked changes in the microfibril angle distribution were observed. The mass fraction of crystalline cellulose in wood (the crystallinity of wood) and the size of cellulose crystallites increased above 150°C. After modification at 230°C for 4 h the thickness of the cellulose crystallites increased from 3.1 to 3.4 nm. Thermal modification had no effect on the orientation of the voids, but an increase in the porosity of the cell wall was observed. The distance between cellulose crystallites was approximately 4.7 nm in hydrated wood and a decrease in order between microfibrils was observed at 160–200°C.

Natural Oil-Based Alkyd-Acrylic Copolymers: New Candidates for Barrier Materials

The feasibility of using alkyd-acrylic copolymers as a barrier material was studied. Copolymers of tall oil fatty acid or rapeseed oil-based alkyd resin and polyacrylates were synthesized and films of these copolymers were prepared. Nuclear magnetic resonance spectroscopy revealed that after copolymerization the proportion of double bonds in alkyd resin was diminished due to grafting reactions. The mechanical properties, such as strength and flexibility, of the copolymer films were tested, and the performance of the films as water, oil, and oxygen barrier was evaluated. An increased amount of alkyd resin made the films more brittle and increased their oxygen permeability, however, at the same time their hydrophobicity was increased.

Encapsulation of 3-iodo-2-propynyl N-butylcarbamate (IPBC) in polystyrene-polycaprolactone (PS/PCL) blends

Abstract Polystyrene (PS, 1), polycaprolactone homopolymers (PCL, 2) and 3-Iodo-2-propynyl n-butylcarbamate (IPBC, 3) were physically mixed in dichloromethane (DCM) and processed into solid microspheres by using emulsion solvent evaporation method. Five different compositions with varying PS/PCL ratio were tested. The phase morphology of the microspheres was studied using Phase imaging atomic force microscopy (AFM) of polished cross-sections. Scanning electron microscopy was utilized to assess the distribution of IPBC in the polymer microspheres. The phase separation of the PS and PCL polymers in solvent cast films was assessed using polarized light optical microscopy of 11 polymer blends (0–100 wt-% PCL in PS). The PS/PCL-IPBC microspheres were incubated in water at RT and the release of IPBC was studied using high performance liquid chromatography (HPLC) at time points 1, 7 and 30 days. The microspheres dispersed in water borne outdoor paint matrix were tested for their antifouling activity against moulds in vitro.

Screening of the effect of biocidal agents released from poly (acrylic acid) matrices on mould growth

Abstract Recently, surface treatment concepts with slow release encapsulated activates have shown to provide a potential approach for the control of biological surface contamination. These new protection concepts respond to the current regulations and demands set for the sustainable development. In this study, screening of the efficacy of biocidal agents – benzoic acid and sodium benzoate – embedded in poly(acrylic acid) matrices was carried out. The efficacy of the polymer systems on mould growth was tested with the blue stain fungus Aureobasidium pullulans and with the mould fungi Trichoderma harzianum and Aspergillus niger. In addition, release of the active agents at different pH was determined in aqueous media. The release tests in aqueous media showed that the release of the active agents is more pronounced at pH higher than 4. The efficacy of the polymer systems according to the present arrangements was dependent on the fungi and the release rate of the active agents from the matrix.

Surface Characteristics and Water Absorption of Sol-Gel Coated Impregnated Paper Pressed onto Plywood

Two silane-based hybrid coatings were developed to modify the surface energy of phenolic resin impregnated paper. The coated paper samples were further pressed onto surfaces of plywood. The surface properties and water repellence of coated paper were investigated by AFM, XPS and water contact angle measurements. The water absorption of plywood with pressed paper was studied by water uptake tests. It was found that the sol-gel coatings had slightly improved the water repellence of the impregnated paper. The water absorption of plywood was also slightly decreased.