Introduction
Low-density cellulosic materials are of interest due to their high inner surface, high toughness, and thermally insulating properties (Aulin et al.
2010; De France et al.
2017; Lavoine and Bergstrom
2017; Srinivasa et al.
2015; Wicklein et al.
2015). At laboratory scale, a bottom-up approach based on cellulose solutions or suspensions of microfibrillated cellulose dried in supercritical carbon dioxide or by means of freeze-drying is most commonly followed. Recently, a top-down approach involving the removal of lignin from solid wood and subsequent freeze-drying has been proposed (Li et al.
2018). Using this approach, anisotropic features similar to special ice-templating (Lee and Deng
2011) and densification methods (Plappert et al.
2017) are obtained. Potential applications of low-density cellulosic solids comprise examples as diverse as thermal insulation (Li et al.
2018; Plappert et al.
2017; Wicklein et al.
2015), packaging (Svagan et al.
2011;
2010;
2008), oil adsorption (Korhonen et al.
2011; Tarrés et al.
2016; Zhang et al.
2014), or supercapacitors (Li et al.
2016; Zu et al.
2016).
As shown by Sehaqui et al. (
2010), (
2011), the density of isotropic porous microfibrillated cellulose-based solids is the main determinant of mechanical strength and stiffness. Beyond that, combinations of microfibrillated cellulose and polymeric binders or matrices may provide further improvements in mechanical stability. Due to the inherent hydrophilicity of native cellulose and due to the fact that microfibrillated cellulose is typically produced by means of fibrillation in aqueous state, water soluble systems are of primary interest. In previous studies (Ago et al.
2016; Svagan et al.
2011;
2008), starch has been successfully used to produce fully biodegradable high performance microfibrillated cellulose foams. Furthermore, water soluble synthetic polyvinyl alcohol (PVOH) has been used to prepare PVOH-cellulose hybrid aerogels (Zheng et al.
2014). When using polymers insoluble in water, solvent exchange with organic solvents is applied (Pircher et al.
2014). Finally, chemical cross linking (Kim et al.
2015; Yang and Cranston
2014) may also provide additional stabilisation.
With regard to chemical cross-linking, furfuryl alcohol (FA) has been repeatedly used in bio-based foams on the basis of either lignin (Tondi et al.
2016) or tannins (Reyer et al.
2016; Szczurek et al.
2016). Modification of solid wood with FA, often referred to as “furfurylation”, has been known since decades. In recent years, new furfurylation processes applying new catalytic systems and process additives have been developed. As reported by Lande et al. (
2008), the properties of furfurylated wood strongly depend on the retention of polymerised furfuryl alcohol (PFA) in the wood structure. At high modification levels, i.e. high retention of PFA, a whole bunch of properties are improved. This particularly involves hardness, resistance to microbial decay and insect attack, dimensional stability as well as bending strength and modulus of elasticity. FA may be considered a green chemical, since it is industrially produced by hydrogenation of furfural, which is itself typically derived from waste bio-mass such as corncobs or sugar cane bagasse (Mariscal et al.
2016). Despite its bio-based character, FA is attractive due to its high reactivity and the option of processing in mixtures with aqueous systems (Gandini et al.
2016). Even though the process of wood furfurylation has been known for a long time, the exact mechanisms of how FA interacts with wood constituents during in situ polymerization are not yet fully understood. Usually, furfurylation is carried out by impregnating wood with a mixture of FA and catalysts after which the impregnated wood is heated to induce polymerisation. As shown by Nordstierna et al. (
2008), aromatic lignin units with hydroxyl groups are highly reactive towards the polymerising PFA chain and the polymerising FA was found to covalently bind to lignin model compounds. Thus, this supports the hypothesis that the furan polymer in furfurylated wood is similarly grafted to wood lignin. Ehmcke et al. (
2017) used cellular ultraviolet microspectrophotometry (UMSP) to analyze chemical alterations of individual cell wall layers of furfurylated radiata pine. The UV-absorbance of modified samples increased significantly compared to the untreated controls, indicating a strong polymerization of the aromatic compounds. Highest UV-absorbances were found in areas with the highest lignin concentration. The UMSP images of individual cell wall layers again suggest the occurrence of condensation reactions between lignin and FA. However, the extent of covalent linkages between PFA and lignin remains largely unknown. Apart from furfurylation of solid wood, several studies reporting on composite materials from cellulose-based fibres and PFA can be found in literature. Pranger and Tannenbaum (
2008) as well as Pranger et al. (
2012) prepared nanocomposites by in situ polymerisation of furfuryl alcohol in the presence of low amounts of cellulose nanowhiskers (CNW). Sulfonic acid residues present at the CNW surface were found to catalyse FA polymerisation. Prepared CNW/PFA nanocomposites exhibited increased thermal stability as well as enhanced breaking strength and toughness as compared to unfilled and filled PFA systems previously described in literature. Another group of authors used cellulose extracted from cotton (Motaung et al.
2016) and flax fibres (Motaung et al.
2018) for the preparation of cellulose/PFA composites. Again, higher thermal stability and better flexural strength and modulus were found for cellulose/PFA composites as compared to the neat PFA matrix.
In the present study, the option of improving the mechanics of porous cellulosic materials by means of in situ polymerisation of FA is evaluated. Two variants of microfibrillated cellulose with known differences in surface chemistry due to differing chemical composition were used in order to ensure optimum compatibility between the cellulosic scaffold and the in situ polymerised FA-based binder.
Conclusions
The results shown in the present study clearly demonstrate that a simple approach of reinforcing porous MFC architectures with PFA by means of in situ polymerisation in aqueous slurry and subsequent freeze-drying is not feasible with standard MFC produced from bleached wood pulp, as there is insufficient wetting between the two phases (cellulose and furfuryl alcohol) of the compound. By contrast, MFLC containing substantial amounts of residual non-cellulosic wood polymers, affords good wettability with furfuryl alcohol and, consequently, a more homogeneous distribution of polymerized FA throughout the lignocellulose scaffold. Although not analysed more closely, the results of the present study thus indicate a strong affinity of FA towards non-cellulosic cell wall constituents during in situ polymerization, ultimately resulting in excellent mechanical reinforcement of porous structures after freeze-drying. Thus modification of MFLC with furfuryl alcohol and subsequent freeze-drying provides a way to prepare lightweight lignocellulosic materials with improved strength and stiffness. In future, such porous materials could provide a bio-based alternative to polystyrene-based foams which are currently extensively used in thermal insulation and packaging applications.
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