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Characterisation of Moisture in Scots Pine (Pinus sylvestris L.) Sapwood Modified with Maleic Anhydride and Sodium Hypophosphite
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Wood Science and Engineering.ORCID iD: 0000-0003-4335-8419
Department of Geosciences and Natural Resource Management, University of Copenhagen, Rolighedsvej 23, 1958 Frederiksberg C, Denmark.
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Wood Science and Engineering.ORCID iD: 0000-0002-7711-9267
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Wood Science and Engineering. Praha 6-Suchdol, Czech University of Life Sciences Prague, Kamýcká 1176, 16521 Prague, Czech Republic.ORCID iD: 0000-0002-5565-6651
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2021 (English)In: Forests, E-ISSN 1999-4907, Vol. 12, no 10, article id 1333Article in journal (Refereed) Published
Abstract [en]

In this study, the wood–water interactions in Scots pine sapwood modified with maleic anhydride (MA) and sodium hypophosphite (SHP) was studied in the water-saturated state. The water in wood was studied with low field nuclear magnetic resonance (LFNMR) and the hydrophilicity of cell walls was studied by infrared spectroscopy after deuteration using liquid D2O. The results of LFNMR showed that the spin–spin relaxation (T2) time of cell wall water decreased by modification, while T2 of capillary water increased. Furthermore, the moisture content and the amount of water in cell walls of modified wood were lower than for unmodified samples at the water-saturated state. Although the amount of accessible hydroxyl groups in modified wood did not show any significant difference compared with unmodified wood, the increase in T2 of capillary water indicates a decreased affinity of the wood cell wall to water. However, for the cell wall water, the physical confinement within the cell walls seemed to overrule the weaker wood–water interactions.

Place, publisher, year, edition, pages
MDPI, 2021. Vol. 12, no 10, article id 1333
Keywords [en]
wood modification, maleic anhydride, sodium hypophosphite, moisture, deuterium exchange
National Category
Wood Science
Research subject
Wood Science and Engineering
Identifiers
URN: urn:nbn:se:ltu:diva-87318DOI: 10.3390/f12101333ISI: 000712389900001Scopus ID: 2-s2.0-85115990726OAI: oai:DiVA.org:ltu-87318DiVA, id: diva2:1599832
Funder
Interreg Öresund-Kattegat-Skagerrak
Note

Validerad;2021;Nivå 2;2021-10-04 (alebob);

Funder: Swedish wood industry; Northern European network for wood science and engineering (WSE); Czech Republic’s funding office (CZ.02.1.01/0.0/0.0/16_019/0000803)

Available from: 2021-10-02 Created: 2021-10-02 Last updated: 2025-03-26Bibliographically approved
In thesis
1. Wood Modification with Maleic Anhydride and Sodium Hypophosphite
Open this publication in new window or tab >>Wood Modification with Maleic Anhydride and Sodium Hypophosphite
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Wood has been a crucial material for construction throughout history. However, due to poor natural durability of wood, it is difficult to use outdoors without any additional treatment. Conventionally, wood has been fully or partially impregnated with preservatives. However, some substances are harmful to mankind and environment, hence, regulated strictly. Therefore, methods for achieving sustainable protection of wood have been required and one method that has been investigated for achieving this has been through chemical modification. 

This doctoral thesis aims to develop a new modification system for solid wood in use class 3. The objective was to develop a wood modification system based on maleic anhydride (MA) and sodium hypophosphite (SHP) that enables exterior use without leaching by weathering. To meet this requirement, the modification should involve formation of stable cross-linking, altering the interaction between moisture and wood, consequently enhancing dimensional stability and biological resistance. 

To test the possibility of using MA and SHP, Scots pine sapwood (Pinus sylvestris L.) was treated with various ratio of chemical reagents, curing temperatures and durations. The treated wood was subjected to repetitive wet-dry cycle to assess its dimensional stability and leachability of chemical reagents. The result indicated formation of a stable cross-linking between wood constituents. 

To further investigate the formation of cross-link, solid-state 13C cross-polarization magic-angle-spinning (CP-MAS) nuclear magnetic resonance (NMR), 31P MAS NMR and X-ray photoelectron spectroscopy (XPS) were employed. The findings indicated that the cross-linking was likely to involve phosphonate (C-P-O) bonds. These results provided a deeper fundamental understanding of the reaction mechanisms between wood, MA and SHP, providing further scope for improved treatment systems in the future.

The impact of the modification on wood-water interactions was analyzed using low-field nuclear magnetic resonance (LFNMR) to study water in the wood at a saturated state. Additionally, the hydrophilicity of cell walls was studied via infrared spectroscopy after deuteration using liquid D2O. The results indicated that the modification reduced the affinity of the wood cell wall to water without altering the number of accessible hydroxyl groups.  

Finally, the modified wood was evaluated for fungal decay resistance, mechanical strength test (bending), and thermal stability. The modification significantly reduced mass loss caused by wood-decaying fungi by limiting the moisture uptake in wood and altering the chemical structure of wood. On the other hand, the modification did not improve resistance to fungal growth on the wood surface, suggesting that nutrient accessibility on surface was not influenced by the modification. A bending test showed that while the modulus of elasticity (MOE) was not affected, modulus of rupture (MOR) decreased to half that of untreated wood. Thermal resistance was improved due to the presence of phosphonate, which can promote the formation of a protective char layer and radical moieties. 

This study demonstrated the potential of modifying wood with MA and SHP to enhance durability, dimensional stability, and fire resistance. The modification formed stable cross-link within the wood components, reducing water interaction and improving resistance to biological degradation. However, the reduction in MOR limits its suitability for load-bearing applications. Despite this, the results suggest that the modified wood could be a viable alternative for non-load bearing exterior applications.

Future research should focus on optimising the modification process by reducing temperature, duration, and solvent use while maintaining performance. Investigating catalysts for the reaction may help address these challenges. Additionally, long-term field testing under real environmental conditions is needed to evaluate the durability and stability of the modified wood. Environmental impact assessments and life cycle analysis will also be crucial for ensuring commercial feasibility and sustainability.

Place, publisher, year, edition, pages
Luleå University of Technology, 2025
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
National Category
Wood Science
Research subject
Wood Science and Engineering
Identifiers
urn:nbn:se:ltu:diva-112139 (URN)978-91-8048-803-7 (ISBN)978-91-8048-804-4 (ISBN)
Public defence
2025-05-27, Luleå University of Technology, Skellefteå, 10:37 (English)
Opponent
Supervisors
Available from: 2025-03-26 Created: 2025-03-26 Last updated: 2025-03-26Bibliographically approved

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Kim, InjeongKarlsson, OlovJones, DennisSandberg, Dick

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