John F. Kadla

Lignin-based carbon fibers for composite fiber applications

Abstract Carbon fibers have been produced for the first time from a commercially available kraft lignin, without any chemical modification, by thermal spinning followed by carbonization. A fusible lignin with excellent spinnability to form a fine filament was produced with a thermal pretreatment under vacuum. Blending the lignin with poly(ethylene oxide) (PEO) further facilitated fiber spinning, but at PEO levels greater than 5%, the blends could not be stabilized without the individual fibers fusing together. Carbon fibers produced had an over-all yield of 45%. The tensile strength and modulus increased with decreasing fiber diameter, and are comparable to those of much smaller diameter carbon fibers produced from phenolated exploded lignins. In view of the mechanical properties, tensile 400–550 MPa and modulus 30–60 GPa, kraft lignin should be further investigated as a precursor for general grade carbon fibers.

Enhancing the enzymatic hydrolysis of lignocellulosic biomass by increasing the carboxylic acid content of the associated lignin

To assess the effects that the physical and chemical properties of lignin might have on the enzymatic hydrolysis of pretreated lignocellulosic substrates, protease treated lignin (PTL) and cellulolytic enzyme lignin (CEL) fractions, isolated from steam and organosolv pretreated corn stover, poplar, and lodgepole pine, were prepared and characterized. The adsorption of cellulases to the isolated lignin preparations corresponded to a Langmuir adsorption isotherm. It was apparent that, rather than the physical properties of the isolated lignin, the carboxylic acid functionality of the isolated lignin, as determined by FTIR and NMR spectroscopy, had much more of an influence when lignin was added to typical hydrolysis of pure cellulose (Avicel). An increase in the carboxylic content of the lignin preparation resulted in an increased hydrolysis yield. These results suggested that the carboxylic acids within the lignin partially alleviate non‐productive binding of cellulases to lignin. To try to confirm this possible mechanism, dehydrogenative polymers (DHP) of monolignols were synthesized from coniferyl alcohol (CA) and ferulic acid (FA), and these model compounds were added to a typical enzymatic hydrolysis of Avicel. The DHP from FA, which was enriched in carboxylic acid groups compared with the DHP from CA, adsorbed a lower mount of cellulases and did not decrease hydrolysis yields when compared to the DHP from CA, which decreased the hydrolysis of Avicel by 8.4%. Thus, increasing the carboxylic acid content of the lignin seemed to significantly decrease the non‐productive binding of cellulases and consequently increased the enzymatic hydrolysis of the cellulose. Biotechnol. Bioeng. 2011; 108:538–548.

The isolation, characterization and effect of lignin isolated from steam pretreated Douglas-fir on the enzymatic hydrolysis of cellulose

Douglas-fir was SO(2)-steam pretreated at different severities (190, 200, and 210°C) to assess the possible negative effect of the residual and isolated lignins on the enzymatic hydrolysis of the steam pretreated substrates. When various isolated lignins were added to the Avicel hydrolysis reactions, the decrease in glucose yields ranged from 15.2% to 29.0% after 72 h. It was apparent that the better hydrolysis yields obtained at higher pretreatment severities were more a result of the greater accessibly of the cellulose rather than any specific change in the non-productive binding of the lignin to the enzymes. FTIR and (13)C NMR characterization indicated that the lignin in the steam pretreated substrates became more condensed with increasing severity, suggesting that the cellulases were adsorbed to the lignin by hydrophobic interactions. Electrostatic interactions were also involved as the positively charged cellulase components were preferentially adsorbed to the lignins.

Quantitative 13C NMR Characterization of Milled Wood Lignins Isolated by Different Milling Techniques

Abstract Milled wood lignins (MWL) prepared from finely milled wood flour produced by different milling techniques were compared by quantitative 13C NMR. Wood meal produced in a Wiley mill was milled for either six weeks in a porcelain rotary mill with porcelain balls, or by two variations of our standard technique. Specifically the Wiley wood meal was milled for one week in the rotary mill followed by 48 h of vibratory ball‐milling with steel balls either in toluene or under a N2 atmosphere. Results showed that the vibratory‐milled samples were similar in structure with the exception that the preparation milled under N2 had higher aliphatic and phenolic hydroxyl contents. The rotary‐milled sample on the other hand had a much lower β‐O‐4′ and hydroxyl content along with a higher degree of condensation and oxidized side chain structures.

Preparation of a thermoresponsive lignin-based biomaterial through atom transfer radical polymerization.

Copolymerization of N-isopropylacrylamide (NIPAM) with technical hardwood kraft lignin (HWKL) was achieved by atom transfer radical polymerization (ATRP) using a selectively modified lignin-based macroinitiator. The degree of polymerization (DP) of polyNIPAM graft side chains was affected by varying the ratio of the DMF/water solvent system from 5:0 to 0:5, and an estimated DP(NIPAM) of >40 was obtained using a ratio of 1:4 (v/v). The thermal decomposition temperature of the lignin-g-polyNIPAM copolymers significantly increased with increasing DP(NIPAM). Likewise, the solubility of the lignin-g-polyNIPAM copolymers in water changed depending on copolymer structure. In both the water-soluble and suspended copolymers, at temperatures above 32 degrees C, the g-polyNIPAM component underwent the typical hydrophilic-to-hydrophobic transition, resulting in the precipitation of the copolymer.

Elucidation of the structure of cellulolytic enzyme lignin

Abstract Cellulolytic enzyme lignin (CEL) and milled wood lignin (MWL) were prepared by three different ball-milling methods. The structure of CEL at various yields was elucidated and compared with MWL using wet chemical analysis, FTIR and solution-state NMR techniques. Results show that ball milling of wood degrades β-O-4 structures in lignin. However, even after extensive ball milling, less than 25% of the β-O-4 structures were degraded. The extent of degradation was less for softwood than for hardwood lignin. Extractable lignin yield, either MWL or CEL, was the best way to assess the extent and effect of ball milling. CEL is preferred over MWL, as it can be isolated in higher yield with less degradation. CEL was isolated at yields ranging from 20% to 86%. Over this range the CEL had similar structures, suggesting that lignin in the secondary wall is uniform in structure. The residual enzyme lignin (REL) was structurally different from CEL and may originate mainly from the middle lamella. In this paper we propose a new procedure for the isolation of lignin for use in structural studies, whereby wood is sufficiently milled and successively extracted to produce three lignin fractions representing the total lignin in wood.

Electrospinning of Technical Lignins for the Production of Fibrous Networks

Abstract Electrospinning is an effective strategy to produce micron and sub-micron diameter fibrous networks from a variety of polymeric systems. Using seven different technical lignins the effect of lignin structure on fiber formation by electrospinning was studied. Surprisingly, none of the technical lignins could be electrospun into continuous fibers, although beaded fiber formation was observed for the softwood Kraft lignin system at high concentration (>50 wt%). However, the addition of poly(ethylene oxide) dramatically affected the electrospinning behavior and fiber formation. For all of the technical lignins a clear transition from electrospray or beaded fibers to uniform fibers was observed upon addition of poly(ethylene oxide); the lignin concentration dependent on poly(ethylene oxide) content. In all of the systems a linear increase in fiber diameter with increasing lignin concentration was observed. At the same concentration, the various lignin solutions had varying viscosities and different electrospinning behavior, that is, fiber diameter and ability to form uniform fibers, suggesting lignin specific structures and intermolecular interactions are influencing solution properties and electrospinning behavior. In fact, specific viscosity versus concentration plots reveal scaling exponents’, η ∼ c7.4–7.8 consistent with a branched polymer participating in intermolecular interactions such as hydrogen bonding or association complexes.

Thermal Decomposition Study of Isolated Lignin Using Temperature Modulated TGA

Abstract Temperature modulated TGA (MTGA) was utilized to study the kinetics of lignin pyrolysis. Three industrial lignin preparations were investigated: softwood kraft lignin, hardwood kraft lignin, and Alcell lignin. Unlike conventional TGA, MTGA provides apparent activation energy (E a ) distribution curve using a single experimental run in a relatively short experimental time. Under Hi-Res conditions using a dynamic heating rate, the activation energies were higher than those determined using a constant heating rate. Likewise, small sample masses provided higher activation energies than those run with large sample mass. These effects can be eliminated by using a relatively large sample mass, > 10 mg. In this study, we discuss the effect of MTGA conditions on calculating E a distribution curves for lignin pyrolysis.

Morphological and chemical variations between juvenile wood, mature wood, and compression wood of loblolly pine (Pinus taeda L.)

Abstract To better understand the within-tree variations between juvenile wood, mature wood, and compression wood, wood from a 35-year-old mature bent loblolly pine was separated into seven groups by different positions in the tree. Morphological and chemical structure analyses, including fiber quality, X-ray diffraction, sugar and lignin content analysis, as well as nitrobenzene oxidation, ozonation, and advanced NMR spectroscopy, were performed. Fiber properties were significantly different for tree-top juvenile normal wood and tree-bottom juvenile normal wood, juvenile normal and mature normal wood, juvenile compression and mature compression wood. However, differences in the chemical structure and composition were less significant within the specific tissues indicated above.

The influence of lignin chemistry and ultrastructure on the pulping efficiency of clonal aspen (Populus tremuloides Michx.)

Abstract The variation in wood chemistry among aspen clones of similar age, harvested from a common site in northern British Columbia, Canada, was evaluated. The aspen clones were evaluated for ease of chemical pulping and differed by as much as 4.5% in pulp yield at a common H-factor. The results demonstrate both the need for understanding the resource and the substantial opportunities that exists in natural population of trees for selecting superior clones for reforestation and afforestation. The syringyl/guaiacyl ratio, as determined by nitrobenzene oxidation, was directly correlated with the ease of pulping, whereas thioacidolysis results were not as predictive. These results were supported by quantitative NMR analysis, which demonstrated differences in the amount of β-O-4/Ar groups and the degree of condensation. Furthermore, it was shown that, in addition to total lignin content, which differed by as much as 5%, structural differences in the lignin may influence pulping efficacy. Among the other parameters evaluated, the distribution of molecular mass and methoxyl content is relevant for pulping. More specifically, among the fractions isolated in this study [milled wood lignin (MWL), MWELsol, and MWELinsol], the insoluble fraction was the most indicative of the pulping efficiency.