Petri Widsten

Adhesion improvement of lignocellulosic products by enzymatic pre-treatment

Enzymatic bonding methods, based on laccase or peroxidase enzymes, for lignocellulosic products such as medium-density fiberboard and particleboard are discussed with reference to the increasing costs of presently used petroleum-based adhesives and the health concerns associated with formaldehyde emissions from current composite products. One approach is to improve the self-bonding properties of the particles by oxidation of their surface lignin before they are fabricated into boards. Another method involves using enzymatically pre-treated lignins as adhesives for boards and laminates. The application of this technology to achieve wet strength characteristics in paper is also reviewed.

LACCASE CATALYZED COVALENT COUPLING OF FLUOROPHENOLS INCREASES LIGNOCELLULOSE SURFACE HYDROPHOBICITY

This work presents for the first time the mechanistic evidence of a laccase-catalyzed method of covalently grafting hydrophobicity enhancing fluorophenols onto Fagus sylvatica veneers. Coupling of fluorophenols onto complex lignin model compounds guaiacylglycerol beta-guaiacyl ether and syringylglycerol beta-guaiacyl ether was demonstrated by LC-MS and NMR. Laccase-mediated coupling increased binding of 4-[4-(trifluoromethyl)phenoxy]phenol (4,4-F3MPP) and 4-(trifluoromethoxy)phenol (4-F3MP) to veneers by 77.1% and 39.2%, respectively. XPS studies showed that laccase-catalyzed grafting of fluorophenols resulted in a fluorine content of 6.39% for 4,4-F3MPP, 3.01% for 4-F3MP and 0.26% for 4-fluoro-2-methylphenol (4,2-FMP). Grafting of the fluorophenols 4,2-FMP, 4-F3MP and 4,4-F3MPP led to a 9.6%, 28.6% and 65.5% increase in hydrophobicity, respectively, when compared to treatments with the respective fluorophenols in the absence of laccase, in good agreement with XPS data.

Effect of high defibration temperature on the properties of medium-density fiberboard (MDF) made from laccase-treated hardwood fibers

High-temperature defibration of hardwood improves the reactivity of hardwood fibers during laccase-catalyzed oxidation. This is due to the progressive breakdown of the lignin polymer with increasing refining temperature, which makes it a more amenable substrate for laccase. Dryprocess 12-mm thick medium-density fiberboards (MDF) of high mechanical strength can be made from fibers treated with laccase in the refiner blowline and without synthetic resins or long laccase incubation times. The internal bond strength and thickness swell properties of the boards improve with an increase in defibration temperature. The improvement of board properties correlates with the number of radicals formed in the fibers on laccase treatment in water suspension. The extent of radical formation depends on the amount of low-molecular weight lignin and other phenolic substances extractable with water or other polar solvents and present in the fibers after defibration. As approximately equal amounts of lignin and other phenolic substances not extractable with acetone are present on the fiber surfaces regardless of refining temperature, differences in fiber surface chemical composition do not account for the different fiber reactivities during oxidation with laccase in water suspension and properties of MDF boards bonded with laccase.

Effect of high-temperature defibration on the chemical structure of hardwood

Summary The present paper aims at elucidating the effect of high-temperature defibration at different temperatures on the bulk and surface chemical properties of defibrated birch, aspen and eucalypt. The results indicate that defibration of these hardwoods results in partial depolymerization of fiber lignin via (homolytic) cleavage of interunit alkyl-aryl (β-O-4) ether bonds. This increases the phenolic hydroxyl content and produces relatively stable (phenoxy) radicals. Syringyl-type lignin is more extensively depolymerized than guaiacyl-type lignin. Defibration generates water-extractable material, which is enriched in hemicellulose-derived carbohydrates and has a substantial content of aromatic compounds rich in phenolic hydroxyl groups. The amount of water-extract and the extent of lignin interunit ether bond cleavage increase with an increase in defibration temperature. The differences between various hardwood species in this respect are small. The surface chemical composition of the fibers differs considerably from their bulk composition, but is not significantly influenced by variations in defibration temperature. Lipophilic extractives cover a large portion of the fiber surface, while the lignin content of lipophilic extractives-free fiber surfaces is 2–3 times as high as the bulk lignin content of the fibers.

A preliminary study of green production of fiberboard bonded with tannin and laccase in a wet process

Abstract A gluing method for fiberboard based on laccase-activated tannin and wood fibers was investigated on a laboratory scale. Oxygen consumption measurements showed that hydrolyzable tannins (tannic acid and chestnut tannin) were more reactive toward laccase than condensed tannins from mimosa and quebracho. Wet-process hardboard prepared with laccase and the most reactive tannin, tannic acid, had superior mechanical strength compared to controls and boards made with laccase alone or laccase and other tannins. The other tannins did not improve mechanical properties more than laccase treatment alone. The addition of wax to the tannic acid-laccase formulation improved the dimensional stability of the boards enough for them to comply with industrial standards, although wax had a negative impact on the mechanical properties. The results cannot be directly applied to dry-process medium-density fiberboard (MDF) production; however, the positive effects of tannin and laccase on hardboard properties also warrant investigations on the green chemistry of MDF production.

Manufacture of Fiberboard from Wood Fibers Activated with Fentons Reagent (H2O2/FeSO4)

Summary Fiberboard was manufactured without synthetic resins from spruce and beech fibers activated by treatment with Fentons reagent (H2O2/FeSO4) and the formation of radicals in the fibers by the action of Fentons reagent was studied. The treatment resulted in a strong improvement of board strength and a large increase in fiber free radical content. The improved adhesion is probably largely due to interfiber bonds formed by reactions of radicals or other reactive groups generated in the fibers by Fentons reagent. The reactivity of spruce fibers in terms of radical formation increased as defibration temperature increased. The thickness swell of the boards depended more on the amount of sizing agent or other additive than on the defibration temperature or fiber reactivity toward Fentons reagent.

Citric acid crosslinking of paper products for improved high-humidity performance

Fibre crosslinking with polycarboxylic acids can be used to improve certain properties of paper products, including wet tensile and compressive strength. In the present work it was proposed that citric acid (CA) crosslinks the cellulosic fibres of linerboard by self-catalysed esterification of cellulosic hydroxyl groups, which makes an additional catalyst unnecessary. An increase in CA dose or curing temperature increased linerboard compressive strength. In CA-treated corrugated board most of the applied CA was esterified with fibres while some CA thermolysis products were also present. A significant portion of the applied CA was unaccounted for. The deficit was attributed to thermolysis to give volatile anhydrides of unsaturated acids. Under cyclic humidity and static compressive loading, CA-treated corrugated boxes showed a greater than three-fold increase in resistance to compressive creep, showing that CA treatment can be used to extend the lifetime of corrugated boxes used for horticultural produce storage.

Factors influencing timber gluability with one-part polyurethanes : studied with nine Australian timber species

Abstract The bulk and surface properties of blocks of nine Australian wood species of commercial importance were investigated to elucidate the factors affecting timber gluability with structural one-component polyurethane adhesives. Cross-lap joints were prepared from freshly sanded blocks and the joints were subjected to creep loading in a condensing humidity environment. The median tensile strength (MTS) of the joints was found to improve with decreasing phenolic extractives content, lower timber density and decreasing lipophilic surface extractives content. The latter was assessed from O/C atomic ratios of the timber surfaces determined by X-ray photoelectron spectroscopy (XPS). The content of bulk lipophilic extractives and lignins and wettability of the surface as determined by the sessile drop method did not reveal significant correlations with the adhesion properties. The adhesion tests indicated significant gluability differences between the species investigated.

Industrial scale evaluation of cationic tannin as a binder for hardboard

Hardboards (HBs) (wet-process high-density fibreboards) were made in an industrial trial using a binder system consisting of cationic mimosa tannin and laccase or just cationic tannin without any thermosetting adhesive. The boards displayed superior mechanical strength compared to reference boards made with phenol–formaldehyde, easily exceeding the European standards for general-purpose HBs. The thickness swell of most of the boards was slightly greater than the standards would allow, so some optimisation is required in this area. The improved board properties appear to be mainly associated with ionic interactions involving quaternary amino groups in cationic tannin and negatively charged wood fibres rather than to cross-linking of fibres via laccase-assisted formation and coupling of radicals in tannin and fibre lignin.