Introduction
As renewable, recyclable, biocompatible and non-toxic substance, cellulose is a highly interesting raw material for manufacturing bio-based products. The utilization of the full potential of this natural polymer, however, often requires its dissolution, which is challenging. As the load-bearing structure in nature, cellulose is organized in the plant cell wall in a hierarchical arrangement that resists degradation. The stiffness of cellulose chains and their close packing make cellulose dissolution a difficult process. Moreover, cellulose is an amphiphilic molecule and therefore strong intra- and intermolecular hydrogen bonding as well as hydrophobic interactions between the molecules affect its solubility (Lindman et al.
2010; Medronho and Lindman
2015). Thus, cellulose is insoluble in water as well as in the most common organic solvents.
Dissolution of cellulose is, however, possible with certain solvents or solvent systems that are able to diffuse into the structure, disrupt the crystalline arrangement of the molecules as well as separate cellulose chains from each other (Ghasemi et al.
2017a,
b). Cellulose dissolution with aqueous sodium hydroxide (NaOH) has a strong industrial potential due to the rapid, non-toxic, low cost and environmentally friendly process. The process has been known already since the early 1900s (Davidson
1934,
1936) and it continues attracting a lot of interest (Cai et al.
2008; Egal et al.
2007; Hagman et al.
2017; Huh et al.
2020; Kihlman et al.
2012; Medronho and Lindman
2015). The dissolution takes place at low temperature (< 0 °C) and hence there is no evaporation of chemicals during the process. The process is fast, however, moderately low degree of polymerization (DP), low cellulose concentration and narrow NaOH concentration range (7–10%) are required (Budtova and Navard
2016; Cai et al.
2008; Egal et al.
2007; Hagman et al.
2017; Isogai and Atalla
1998; Medronho and Lindman
2015). Moreover, semidilute solutions (e.g. 5% cellulose in 9% NaOH solution) tend to gel with time and increase in temperature (Liu et al.
2011; Pereira et al.
2018; Roy et al.
2003). Several mechanisms for cellulose dissolution in aqueous NaOH have been proposed. One of the theories suggests that at low temperatures NaOH forms hydrates with water that may permeate into the structure of the cellulosic material and detach individual cellulose chains from each other (Cai et al.
2008; Egal et al.
2007). On the other hand, it has been shown that cellulose deprotonates in aqueous NaOH (Bialik et al.
2016; Isogai
1997). Charging up polymers is expected to increase their solubility and thus the net charge of dissociated cellulose can play a significant role in the dissolution of this polymer (Kihlman et al.
2013).
Cellulose dissolution in aqueous NaOH and the stability of the solution against gelation can be enhanced with certain additives, such as zinc oxide (ZnO) (Kihlman et al.
2013; Liu et al.
2011; Yang et al.
2011). Despite the clear improvement of cellulose solubility with the addition of ZnO observed in practice, the exact role of the added ZnO is currently under debate. ZnO forms zincate (Zn(OH)
42−) in the strongly alkaline NaOH solution, and Yang et al. (
2011) have suggested that the zincate improves cellulose dissolution by forming even stronger hydrogen bonds with it while Kihlman et al. (
2013) have proposed that the zincate associates to cellulose enhancing the dissolution by further charging up the molecules. On the other hand, it might be that a Zn-cellulose complex is formed in the alkaline environment (Väisänen et al.
2021). Furthermore, Liu et al. (
2011) have proposed that ZnO acts as water “binder” stabilizing cellulose solutions.
However, even with the addition of ZnO, dissolution of wood fibers is poor without a pretreatment, or “activation”, prior to the dissolution process (Cuissinat and Navard
2006; Kihlman et al.
2012; Väisänen et al.
2021). The high DP of cellulose has been shown to be one of the most important factors hindering its dissolution in the alkaline system (Isogai and Atalla
1998; Yamashiki et al.
1990; Yang et al.
2011). However, it is not the only factor affecting the dissolution. It has also been shown that in the cell wall, the longer the time from the cellulose deposition is, the more difficult it is to dissolve the cellulose (Le Moigne et al.
2008). In addition, thick-walled compression wood cells and summerwood cells might be difficult to dissolve (Jardeby et al.
2004). Thus, the structural organization of the cell wall layers and/or the presence of non-cellulosic material in the cell wall have an effect on the dissolution (Le Moigne et al.
2008; Le Moigne and Navard
2010). Indeed, when plant fibers are placed in the aqueous NaOH solvent, heterogeneous swelling along the fiber length, a phenomenon called “ballooning”, is observed. This phenomenon was discovered already a long time ago (Nägeli
1864). Based on more recent studies, Cuissinat and Navard (
2008) have proposed the mechanism for dissolution by ballooning to be the following: when the solvent permeates the fibers, cellulose in the secondary wall dissolves causing heterogeneous swelling of the primary wall and the formation of balloons finally bursting them followed by the dissolution of the unswollen sections of the fibers and, in the end, the balloon membrane scraps. In order to enhance the dissolution of cellulosic fibers many types of pretreatment methods have been employed including steam explosion, hydrothermal, chemical and enzymatic treatments (Kihlman et al.
2012,
2013; Le Moigne and Navard
2010; Peleteiro et al.
2015; Trygg and Fardim
2011; Yamashiki et al.
1990; Wawro et al.
2009).
In this paper, the effect of various hydrolytic pretreatments on wood pulp dissolution in the aqueous NaOH–ZnO solvent system is investigated. The dissolution of the pulps is evaluated both visually with an optical microscope as well as at the molecular level based on their reactivity with 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxo-piperidium (4-AcNH-TEMPO
+). The method for studying the reactivity of cellulose is based on rapid and selective oxidation of the hydroxymethyl (-CH
2OH) groups of cellulose to carboxyl groups (–COOH) by 4-AcNH-TEMPO
+ in mild conditions (pH 9, room temperature) (Khanjani et al.
2017; Väisänen et al.
2021). The method enables studying the reactivity of cellulose quantitatively and thus assessing the dissolution at the molecular level. In theory, fully dissolved (molecularly dispersed) cellulose molecules should be able to react freely with 4-AcNH-TEMPO
+ resulting in complete oxidation of the –CH
2OH groups of cellulose. Finally, pulp dissolution was evaluated in relation to the fiber properties (i.e. the extent of fibrillation, amount of fines and fiber width, coarseness, and length) as well as the hemicellulose and cellulose contents and the viscosity of the pulps.
Conclusions
The effect of various types of hydrolytic pretreatments on alkaline dissolution of a never-dried softwood kraft pulp was studied. The dissolution of the pulps in the NaOH–ZnO solvent system was evaluated both visually with optical microscopy and at the molecular level based on their reactivity with 4-AcNH-TEMPO+. The medium consistency hydrolysis was successful in increasing the solubility of the fibers. The high consistency hydrolysis increased fiber solubility to some extent but with extended treatment time (50 min) the fibers formed aggregates and their dissolution became poor. This phenomenon could be overcome by mechanical refining of the fibers after the hydrolysis. Moreover, the unhydrolyzed reference pulp had a high degree of oxidation when reacting with 4-AcNH-TEMPO+ (> 70%) despite its poor dissolution in the NaOH–ZnO system. Thus, it seems that the solvent is able to disrupt cellulose crystallinity in the S2 layer causing this pulp to swell but not dissolve. For complete dissolution of the fibers, dissolution of the more resistant outer layers of the fiber wall are needed. Comparison of the pulp viscosities over their degree of oxidation showed that the pulp started to dissolve when the viscosity was decreased to below ca. 400 ml/g (i.e. DP = ~ 550). This is in line with the fiber wall structure in the S1 layer consisting of elementary fibrils assembled in helical bundles. The length of cellulose chains with the DP of 550 is below the mean period of the helical twists in the bundles. Thus, it seems that in order to detach individual cellulose chains from each other, they need to be short enough to overcome the physical barrier formed by the helical twists of the fibril bundles in the S1 layer. The highest solubilities of the studied pulps were observed for the medium consistency hydrolyzed pulp MC220 reaching over 90% degree of oxidation and the high consistency hydrolyzed pulp after the mechanical refining, HC250, with the degree of oxidation over 80%. Furthermore, when pulps with similar viscosities where compared against each other, the ones with the higher glucomannan contents formed gels over time. This was observed also for the pulp MC220 with the lowest viscosity and the highest solubility of the studied pulps.
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