ABSTRACT
Copper is a common component in wood preservatives and is used to protect the wood against fungal degradation. Previous research has shown that the Cu++ oxidation state provides the best wood protection, and Cu++ is widely believed to be the oxidation state of most copper within treated wood. A recent study using X-ray absorption near edge spectroscopy (XANES) reported high amounts of Cu+ in wood that had been in contact with corroded fasteners. This study uses XANES to examine the copper oxidation states in wood treated with several different wood preservatives as a function of time after treatment. In contrast with previous literature which focused on the fixation reaction in the first few hours after treatment, this paper examines the oxidation state of Cu in treated wood at longer times (up to 1-year) after treatment. The results showed in nearly all cases, Cu was in the Cu++ oxidation state to within the measurement uncertainty. Cu XANES patterns taken approximately 1-year after treatment showed no discernable differences between preservative systems, indicating that regardless of the starting treatment the final Cu speciation is the same within one year. The results confirm previously held beliefs about the Cu oxidation states in wood and give further insights into the corrosion mechanism of metals embedded in treated wood.
Subject(s)
Copper/chemistry , Wood/chemistry , X-Ray Absorption Spectroscopy , Oxidation-ReductionABSTRACT
Our future bioeconomy depends on increased utilization of renewable lignocellulosic biomass. Controlling the diffusion of chemicals, such as inorganic ions, within secondary plant cell walls is central to many biomass applications. However, insufficient understanding of intra-cell-wall diffusion within secondary plant cell walls is hindering the advancement of many lignocellulosic biomass applications. In this work, X-ray fluorescence microscopy was used to measure diffusion constants of K+, Cu2+, and Cl- diffusing through loblolly pine (Pinus taeda) cell wall layers under 70%, 75%, or 80% relative humidity (RH). Results revealed that diffusion constants increased with RH, the larger Cu2+ diffused more slowly than the K+, and the Cl- diffusion constant was the same as that for the counter cation, indicating cations and anions diffused together to maintain charge neutrality. Comparison with electrical conductivity measurements showed that conductivity is being controlled by ion mobility over these RH. The results further support that intra-cell-wall diffusion of inorganic ions is a Fickian diffusion process occurring through rubbery amorphous polysaccharides, which contradicts previous assertions that intra-cell-wall diffusion is an aqueous process occurring through water pathways. Researchers can now utilize polymer science approaches to engineer the molecular architecture of lignocellulosic biomass to optimize properties for specific end uses.
ABSTRACT
The elastic properties of pit membranes are reported to have important implications in understanding air-seeding phenomena in gymnosperms, and pit aspiration plays a large role in wood technological applications such as wood drying and preservative treatment. Here we present force-displacement measurements for pit membranes of circular bordered pits, collected on a mesomechanical testing system. The system consists of a quartz microprobe attached to a microforce sensor that is positioned and advanced with a micromanipulator mounted on an inverted microscope. Membrane displacement is measured from digital image analysis. Unaspirated pits from earlywood of never-dried wood of Larix and Pinus and aspirated pits from earlywood of dried wood of Larix were tested to generate force-displacement curves up to the point of membrane failure. Two failure modes were observed: rupture or tearing of the pit membrane by the microprobe tip, and the stretching of the pit membrane until the torus was forced out of the pit chamber through the pit aperture without rupture, a condition we refer to as torus prolapse.
