Alkaline peroxide mechanical pulping of novel Brazilian Eucalyptus hybrids

dos S. Muguet, M. C., Colodette, J. L., and Jääskeläinen, A.-S. (2012). "Alkaline peroxide mechanical pulping of novel Brazilian Eucalyptus hybrids," BioRes. 7(3), 3823-3836.

Abstract

Eucalyptus wood is among the most important biomass resource in the world. Wood mechanical defibration and fibrillation are energy-intensive processes utilized not only to produce pulp for papermaking, but also to produce reinforcement fibers for biocomposites, nanocellulose, or pretreat lignocellulosic material for biofuels production. The structural features of different Eucalyptus hybrids affecting the refining energy consumption and produced fiber furnish properties were evaluated. The defibration and fiber development were performed using an alkaline peroxide mechanical pulping (APMP) process, which included chelation followed by an alkaline peroxide treatment prior to wood chip defibration. Despite the similar wood densities and chemical compositions of different Eucalyptus hybrids, there was a clear difference in the extent of defibration and fibrillation among the hybrids. The high energy consumption was related to a high amount of guaiacyl lignin. This observation is of major importance when considering the optimal wood hybrids for mechanical wood defibration and for understanding the fundamental phenomena taking place in chemi-mechanical defibration of wood.

Download PDF

Full Article

Alkaline peroxide mechanical pulping of novel brazilian eucalyptus hybrids

Marcelo C. dos S. Muguet,^a,* Jorge L. Colodette,^b and Anna-Stiina Jääskeläinen^c

Keywords: Alkaline peroxide mechanical pulping; APMP; Defibration; Energy consumption; Eucalyptus; Hybrids; Lignin structure; Pulp properties

Contact information: a: Aalto University, School of Chemical Technology, Department of Forest Products Technology, Vuorimiehentie 1, Espoo, Finland, 02150; b: Universidade Federal de Viçosa, Laboratório de Celulose e Papel, Campus UFV, Viçosa, Minas Gerais, Brazil, 36570-000; c: Technical Research Centre of Finland, VTT, Tietotie 2, Espoo, Finland, 02044; *Corresponding author: marcelo.muguet@aalto.fi, marcelomuguet@gmail.com

INTRODUCTION

Eucalyptus sp. is one of the most important lignocellulosic fiber sources worldwide and its role is increasing steadily, while the need for biomass as a renewable raw material also is expanding. The major interest in Eucalyptus wood originates from its low production cost in certain regions, mainly because of high forest productivity. The increasing understanding of its application in various paper grades makes Eucalyptus one of the preferred fiber raw material worldwide (Magaton et al. 2009). Part of the success of the Brazilian forest industry relates to its intensive breeding program, focusing on Eucalyptus hybrids. Brazilian breeders are investing heavily in the potential of Eucalyptus globulus, due to its adequate wood density, fiber length, chemical composition, and lignin structure in relation to other commercial Eucalyptus species (Rencoret et al. 2008).

Some other generations of Brazilian-grown Eucalyptus hybrids have already been evaluated for kraft pulping and papermaking (Gomide et al. 2005), but research on the mechanical defibration of Eucalyptus wood species is still lacking. Eucalyptus woods have already been used in mechanical pulping, but in terms of process design and post-pulping bleachability, only two processes are suitable for high brightness paper grades and packaging: alkaline peroxide mechanical pulping (APMP) and alkaline sulfite mechanical pulping (CTMP) (Xu and Sabourin 1999). The APMP process is an interesting pulping method for Eucalyptus woods; especially when producing suitable high-brightness papers, since the wood chips can be fully bleached prior to refining (Cort and Bohn 1991). The APMP process has several pre-treatment stages prior to the actual defibration. In the first one, chelants are used to remove metals (Area and Kruzolek 2000). The metals removal is necessary, since hydrogen peroxide (used on the further pre-treatment stages) is decomposed by their presence, especially manganese (Qiu et al. 2003). The process presents high flexibility in processing wood of variable qualities and it delivers fibers of higher density, tear and tensile strength when compared to CTMP fibers (Xu and Sabourin 1999).

Mechanical pulping is an energy-intensive process, and methods for reducing energy demand during refining have been largely investigated. For example, the application of enzymatic treatments (Hart et al. 2009), the reduction of raw materials variability (Dundar et al. 2009), and the use of chemical treatments (e.g. alkaline hydrogen peroxide) are among the many attempts to decrease refining energy demand. However, it is obvious that wood composition and ultrastructure have a distinct impact on the energy consumption. Therefore, understanding the fundamental phenomena of the defibration process and determining the variables affecting the energy consumption are crucial to establishing the possibilities to reduce the energy consumption.

The objective of this study was to evaluate the feasibility of a new generation of top-level Eucalyptus hybrids for APMP production. The focus was to investigate the effect of structural components of wood on energy consumption, fiber, and pulp properties.

EXPERIMENTAL

Four different hybrids of Brazilian-grown Eucalyptus trees derived from the Genolyptus genetic breeding program were used in this study. The wood samples were coded based on the following crossings: E. grandis x [E. urophylla x E. globulus] (G1xUGL), E. urophylla x E. urophylla (U1xU2), [E. dunnii x E. grandis] x E. urophylla (DGxU2) and E. grandis x E. urophylla (REF) (Table 1). The hybrid REF was chosen to be the reference since it was already planted and used as an industrial fiber source. The others are being evaluated for their potential as a wood source for the pulp and paper industries.

Table 1. Wood Chemical and Physical Characterization

* Gluc= Glucans, Xyl= Xylans (as backbone), Oth= Other hemicelluloses, Klas= Klason, ASL= Acid Soluble Lignin, Tot= Total Lignin, S/G= Syringyl-to-Guaiacyl Ratio, UA= Uronic Acids, Dens= Density

The carbohydrate composition was analyzed by HPAEC-PAD after acid hydrolysis, following the procedure described by Wallis et al. (1996). Total uronic acids were evaluated according to Scott (1979). Klason and acid soluble lignins were measured according to Gomide and Demuner (1986) and Goldschimid (1971), respectively. Lignin content was defined as the sum of Klason and acid soluble lignin as described by Dence (1992). Syringyl/Guaiacyl ratio (S/G) was evaluated according to Lin and Dence (1992). Acetyl groups were evaluated according to Solar et al. (1987). Wood density was evaluated according to TAPPI standard T258 om-06.

The APMP process was carried out with a pre-vaporization stage of 20 minutes and double-stage chemical impregnation (Table 2). The first impregnation stage consisted of the application of NaOH and DTPA. It was carried out in a press apparatus that works with compression forces of ca. 14 MPa. After the chips were squeezed, the chemicals were added, and after that, the pressure was released so that the chemicals penetrated the chips. The chelation stage was run at 25^oC, for 20 minutes, with a liquor-to-wood ratio (L/W) of 4:1. The liquor was then pressed out of the chips and collected for further analyses. The second impregnation stage consisted of the application of alkaline hydrogen peroxide and stabilizers. It was carried out following the same pressing procedure of the first stage, but then transferred in a plastic bag and placed in a warm bath under 60 °C, for 60 minutes, and a L/W ratio of 4:1. The liquor was then pressed out of the chips and collected for further analyses. After pressing, the chips were ca. 43% consistency.

Mechanical pulping was carried out in a wing defibrator, consisting of four static blades, refining gap between blades, and inner refiner wall of 2.5 mm, ca. 750 rpm, 100 o.d. grams per run per sample, at ca. 43% consistency, temperature of 130 °C, and refining times of 4, 7, 10, and 13 minutes. The liquors obtained after each impregnation stage were subjected to pH and hydrogen peroxide concentration (iodometric titration) measurements. Handsheets were prepared (ISO 5269-1:2005) and tested for grammage (ISO 536:1995), density (ISO 534:1988), tear strength (ISO 1974:1990, Elmendorf method), tensile index (SCAN-P38), and optical properties (ISO 2470:1999 and ISO 9416:1998). X-ray photoelectron spectroscopy (XPS) measurements were done according to Johansson and Campbell (2004), and surface lignin concentration was calculated according to Laine et al. (1994). Fiber morphological analyses were done with a FiberLab analyzer (Metso Automation, Finland).

Table 2. Chemical Charges (kg/odt) Applied During Double-Stage Impregnation

RESULTS AND DISCUSSION

APMP Experiments

Double-stage impregnation

In the APMP process, the wood chips were impregnated in two stages: first using chelating agents to remove metals, followed by a second impregnation with alkaline hydrogen peroxide to bleach the wood chips and reduce refining energy consumption. No significant differences were seen among the various wood samples regarding either the end pH of the first and second impregnations or hydrogen peroxide consumption in the second impregnation (Table 3). This was an indication that the pre-treatments behave similarly for all wood samples.

Table 3. Characterization of Liquors from Both Pre-Impregnation Stages

Refinings

High refining energy consumption is a key factor limiting the utilization of mechanical wood defibration (Francis et al. 2002). In addition, high energy demand is also problematic in other types of defibration processes, such as microfibrillated cellulose (MFC) production. For example, Spence et al. (2011) showed that energy consumption during the production of MFC can be decreased by choosing an appropriate method. In addition, mechanical pulps can be used as raw material for MFC production, and MFC-containing aromatic lignin may reduce production costs and result in new uses and products (Spence 2011). Therefore there is a need to determine the fundamental phenomena affecting the required defibration energy and to find novel methods for its reduction. The use of chemicals has been said to reduce energy consumption (Xu and Sabourin 1999), as well as choosing a suitable wood for such processes. Although the wood characterization, the pre-refining chemical treatments, and progress in the specific energy consumption did not show large differences among the wood hybrids, the development of drainage properties among the samples varied significantly (Fig. 1). It is worth pointing out that the refiner used in this study consumes higher amounts of energy when compared to disc or pilot scale refiners (Jones and Richardson 2000, 2001; Xu and Sabourin 1999). It was assumed that, at least as an approximation, the total applied energy with different refining systems will be proportional to the energy that manifests itself as changes to the fibers. Nevertheless, the hybrid G1xUGL shows the best refinability among all hybrids, since it reached lower freeness levels than all the other hybrids at similar energy levels. This refinability could not be explained by the morphological properties, since Prinsen et al. (2012) showed that there are no relevant differences on fiber width among the same hybrids studied in this work. Moreover, recent studies (Rusu et al. 2011) show that thicker cell walls need less energy to reach a given freeness, however such differences are not enough to explain different behavior between the evaluated species (pine and spruce).

Fig. 1. Specific energy consumption (S.E.C.) vs. freeness for all four Eucalyptus hybrids pulp samples

Pulp Physical and Mechanical Properties

If the mechanical fiber furnish is used for paper applications, an ideal mechanical pulp produces paper sheets with high opacity, brightness, bulk, and smoothness, as well as a suitable pore structure at low grammage without excessive use of reinforcement pulp (Lönnberg 2009). On the other hand, if short-fiber pulp is used for composite reinforcement, properties such as aspect ratio and number of fibers per gram are of major importance. Using short fibers and consequently a high number of fibers per gram, the fiber-free areas in the composite is decreased, as well as the aspect ratio, which enhances the fiber dispersion (Chung 2005). Tonoli et al. (2010) studied the potential of Eucalyptus fibers as cement reinforcement. They observed that such fibers were suitable as reinforcement due to low-energy refining and a higher number of reinforcing elements, providing effective crack bridging and contributing to the maintenance of the mechanical performance of the composite after accelerated ageing cycles.

As illustrated in Fig. 1, relevant differences in refinability were noted among the four Eucalyptus hybrids and such differences can play an important role regarding paper properties. Table 4 shows that the density of paper sheets increases with longer refining. The main reasons are that fibers tend to be more flexible, increasing the relative bonding area. In addition, external fibrillation tends to increase the interfiber bonding formation, leading to a more closed and dense fiber network.

Table 4. Summary of Physical, Mechanical, and Optical Properties of Pulp Samples Derived From all Four Eucalyptus Hybrids

Tensile index can indicate how the paper will behave during its manufacturing process, and it can be highly affected by bonding strength between fibers, fiber length, and stiffness. It is shown in Table 4 that in general, all four hybrids produced weaker sheets when compared to Eucalyptus chemical fibers at the same freeness levels (Muguet et al. 2011). Mechanical pulps can have a higher tensile index than chemical pulps at the same sheet density (Xu and Zhou 2007), but in this study the sheet densities were quite low because of the relatively low refining levels (Fig. 1). However, the results are comparable with the observations of Xu and Sabourin (1999).

Increased fiber strength obviously increases the tear strength. Table 4 shows that fibers from G1xUGL are much stronger than DGxU2 at same refining energy level. In addition, fiber length also influences e.g. tear index (Kärenlampi, 1996). Such influence can be seen when comparing Table 4 and Table 6. G1xUGL shows relatively higher fiber length than DGxU2, which might have positively affected the tear index values.

Tear index is better interpreted when correlated to tensile index (Fig. 2). A great correlation index was found among all samples, indicating that if some of the hybrids were refined to lower freeness levels (Fig. 1), they could have reached similar values, showing distinctions in refinability.

Fig. 2. Tensile index vs. tear index for all four Eucalyptus hybrids pulp samples

To illustrate the differences in refinability, the results from all hybrids were plotted together in Fig. 3, revealing high correlation indexes for sheet density, tensile index, and tear index with freeness. This indicated that with more intensive refining, poorly refinable hybrids could achieve similar properties to their refinable counterparts. However, this would require more energy for the refining process. Some studies have confirmed the fact that differences in wood quality can impact the refining process and pulp quality (Dundar et al. 2009; Jones et al. 2005), but as the hybrids do not show eminent differences among themselves regarding absolute chemical composition, such differences might be related to the wood ultrastructure and/or the fiber wall polymer structure.

Fig. 3. Sheet density, tensile, and tear index vs. freeness for all four Eucalyptus hybrids pulp samples

Surface Properties and Fiber Morphology

The surface composition of fibers defines the fiber bonding properties in papermaking and the compatibility with the matrix in composite production. Therefore, the surface lignin content was evaluated with X-ray photoelectron spectroscopy, which is a well-known surface analytical tool for wood fibers (Johansson and Campbell 2004; Laine et al. 1994). The surface lignin content was not significantly affected by the refining time for any of the hybrids. However, the differences among the hybrids were evident (Table 5). The most important aspect is that even though no clear trend was seen among refinings, all values of surface lignin content are substantially higher than the original lignin content of the woods (Table 1 and Table 5). This result agreed with the findings for spruce chemi-mechanical pulps by Koljonen et al. (2003) and indicated that the defibration took place on the middle lamella region, which is expected for chemi-mechanical processes (Fig. 4, adapted from Franzén 1986).

Fig. 4. Defibration mechanism of typical APMP process and illustration of lignin units localization on Eucalyptus wood (adapted from Franzén 1986, Watanabe et al. 2004). ML = Middle Lamella; P = Primary wall; S1, S2, S3 = Secondary wall layers; G = Guaiacyl lignin units; S = Syringyl lignin units.

Table 5. Surface Lignin Content of Fibers as Analyzed by XPS

As the defibration process took place mostly at the middle lamella, where the lignin concentration is higher, it was expected that the lignin structure played an important role. The content of guaiacyl lignin in the wood samples varied notably among the samples (Table 1), whereas the lignin content was almost constant. It was noted that guaiacyl units content had a negative effect on the energy consumption in order to reach a certain freeness (Fig. 5). In Eucalyptus globulus, for example, Watanabe et al. (2004) showed that guaiacyl units are mainly located in the middle lamella and vessels walls (as illustrated in Fig. 4). This concept for hardwoods was also shown in other studies (Musha and Goring 1975). Due to the fact that there is an absence of methoxyl groups, the amount of cross-linking increases. In addition, these lignin units are known to increase the softening temperature of wood lignin (Olsson and Salmén 1997). A low S/G ratio has also been shown to impair chemical pulping processes (González-Vila et al. 1999; del Río et al. 2005; Pinto et al. 2005; Stewart et al. 2006; Gomes et al. 2008; Santos et al. 2011). In this study, the guaiacyl content likely affected the softening temperature of the different hybrids, as well as decreased the reactivity of lignin with the alkaline peroxide treatment, requiring more energy to defibrate the chips, and reaching a certain freeness level (450 CSF). Prinsen et al. (2012) revealed that the highest amount of β-O-4 linkages exist between lignin units for the G1xUGL hybrid, whereas DGxU2 had the lowest amount. This corroborates the increased reactivity of the G1xUGL hybrid.

Fig. 5. Influence of guaiacyl units content on the refining energy demand to reach a given freeness of 450 CSF for all four Eucalyptus hybrids woods

When plotting the physical and mechanical properties as one set, it was observed that the correlation between surface lignin content and paper properties was weak (Fig. 6). The low correlation indices can be attributed to the fact that besides the number and strength of formed interfiber hydrogen bonds, the structure and intrinsic strength of the fibers are also important to the properties of the finished paper. Thielemans and Wool (2005) studied the deposition of kraft lignin onto natural fiber surfaces. Such lignin samples contain a large amount of hydroxyl groups not found in native lignin, such that these polar ends would interact favorably with the cellulosic fiber. The effect of lignin deposition was positive when producing resin composites due to a better incorporation of lignin to the hydrophobic matrix. Thus, chemi-mechanical pulp fibers with high surface lignin, which was somehow modified by a previous alkaline treatment, could possess potential as the reinforcement phase of composites. The surface extractives content of the fibers were very low (2.5 to 4%) when compared with other mechanical and chemi-mechanical pulps (Koljonen et al. 2003; Johansson et al. 2004; Zhou et al. 2006) and no correlation between the fiber properties and surface extractives content were observed.

Fig. 6. Sheet density, tensile, and tear index vs. surface lignin content for all four Eucalyptus hybrids pulp samples

The morphological properties of single fibers did not show large differences in the fiber length among all pulp samples (Table 6). However, tear strength depends on fiber length, besides fiber strength (Kärenlampi 1996), as discussed in the previous section. Nevertheless, such values are in line with fiber length distribution of the same Eucalyptus hybrids’ wood fibers (Prinsen et al. 2012).

Table 6. Fiber Length Measurements of Pulp Fibers

Other important fiber properties for bonding strength, such as curl and fibrillation index, were impacted by the amount of lignin on the fiber surface. Figure 7 shows that at a tensile index of 6 kNm/kg, the fibrillation and curl index decrease with increasing surface lignin content.

Fig. 7. Surface lignin content vs. curl index and fibrillation index for sample with a tensile index of 6 kNm/kg for each Eucalyptus hybrids pulp samples

The surface lignin decreased the area of carbohydrates that would then fibrillate, and stiffened the fibers at the same time, leaving them more aligned (low curl index). The fact that the fibers were more aligned tended to compensate the lower fibrillation indices, which could explain the similarities in tensile index values.

CONCLUSIONS

The chemi-mechanical wood defibration process is a suitable method for the novel Brazilian Eucalyptus hybrids.
The hybrid with E. globulus genome (G1xUGL) showed better performance in all technical properties evaluated than the other Eucalyptus hybrids.
The major differences observed for the four hybrids were in the amounts of refining energy needed to reach a certain fiber development level.
There were indications that the lignin structure, especially the guaiacyl units content, has a definite role in increasing the energy consumption of the defibration process.

ACKNOWLEDGMENTS

The authors would like to acknowledge the financial support from the Academy of Finland (Effect of fibre wall chemistry on energy demand in wood defibration, DEFIBRE) and the Conselho Nacional de Desenvolvimento Científico e Tecnológico – CNPq – Brazil. The authors would also like to acknowledge José Maurício Lino, for the wood chemical characterization, Heikki Tulokas, for his help during refining experiments, Dr. Leena-Sisko Johansson and Dr. Joe Campbell for the XPS measurements, Dr. Kyösti Ruuttunen for inspiring discussions, and Dr. Justin O. Zoppe for the linguistic revision.

REFERENCES CITED

Area, M. C., and Kruzolek, C. (2000). “Aplicación de variantes del proceso de pulpado al peróxido alcalino a Eucalyptus grandis de 6 y 15 años,” Congreso Iberoamericano de Investigacion en Celulosa y Papel- CIADICYP, Missiones, Argentina.

Chung, D. D. L. (2005). “A review of Australian research into natural fibre cement composites,” Cement and Concrete Comp. 27, 518-526.

Cort, C. J., and Bohn, W. L. (1991). “Alkaline peroxide mechanical pulping of hardwoods,” Tappi J. 74(6), 79-84.

del Río, J. C., Gutiérrez, A., Hernando, M., Landín, P., Romero, J., and Martínez, Á. T. (2005). “Determining the influence of eucalypt lignin composition in paper pulp yield using Py-GC/MS,” J Anal Appl Pyrol. 74, 110-115.

Dence, C. W. (1992). “The determination of lignin,” In: Methods in Lignin Chemistry, S. Y. Lin and C. W. Dence (eds.), Springer Verlag, Berlin.

Dundar, E., Laperrière, L., and Ding, F. (2009). “Decreasing specific energy of thermomechanical pulps from reduction of raw materials variability,” Tappi J. 8(9), 23-29.

Francis, D. W., Towers, M. T., and Browne, T. C. (2002). Energy Cost Reduction in the Pulp and Paper Industry – An Energy Benchmarking Perspective, Pulp and Paper Technical Association of Canada.

Fránzen, R. (1986). “General and selective upgrading of mechanical pulps,” Nordic Pulp Pap. Res. J. 1, 4-13.

Goldschimid, O. (1971). “Ultraviolet spectra,” In: Lignins, Occurrence, Formation, Structure, and Reactions, K. V. Sarkanen and C. H. Ludwig (eds.), John Wiley and Sons, New York, 241-266.

Gomes, F. J. B., Gouvêa, A. F. G., Colodette, J. L., Gomide, J. L., Carvalho, A. M. M. L., Trugilho, P. F., Gomes, C. M., and Rosado, A. M. (2008). “Influence of content and S/G relation of the wood lignin on kraft pulping performance,” O. Papel 69, 95-105.

Gomide, J. L., Colodette, J. L., Oliveira, R. C., and Silva, C. M. (2005). “Technological characterization of the new generation of Eucalyptus clones in Brazil for kraft pulp production,” Rev. Árvore 29, 129-137.

Gomide, J. L., and Demuner, B. J. (1986). “Determinação do teor de lignina em material lenhoso: Método klason modificado,” O Papel 47, 36-38.

González-Vila, F. J., Almendros, G., del Río, J. C., Martín, F., Gutiérrez, A., and Romero, J. (1999). “Ease of delignification assessment of wood from different Eucalyptus species by pyrolysis (TMAH)-GC/MS and CP/MAS ¹³C-NMR spectrometry,” J Anal Appl Pyrol. 49, 295-305.

Hart, P. W., Waite, D. M., Thibault, L., Tomashek, J., Rousseau, M.-E., Hill, C., and Sabourin, M. J. (2009). “Refining energy reduction and pulp characteristic modification of alkaline peroxide mechanical pulp (APMP) through enzyme application,” Tappi J. 5, 19-25.

Johansson, L.-S., and Campbell, J. (2004). “Reproducible XPS on biopolymers: Cellulose studies,” Surf. Int. Anal. 36, 1018-1022.

Johansson, L.-S., Campbell, J., Koljonen, K., Kleen, M. and Buchert, J. (2004). “On surface distributions in natural cellulosic fibers,” Surf Interface Anal. 36, 706-710.

Jones, T. G. and Richardson, J. D. (2000). “Chemimechanical pulping of New Zealand-grown Eucalyptus fastigata,” Appita J. 53, 398-403.

Jones, T. G. and Richardson, J. D. (2001). “Chemimechanical pulping of New Zealand-grown Eucalyptus regnans,” Appita J. 54, 265-271.

Jones, T. G., Song, G. G., and Richardson, J. D. (2005). “Effect of chipper setting on chip size distribution and mechanical pulp properties,” Appita J. 58, 56-63.

Kärenlampi, P. P. (1996). “The effect of pulp fiber properties on the tearing of paper.” Tappi J. 79, 211-216.

Koljonen, K., Österberg, M., Johansson, L.-S., and Stenius, P. (2003). “Surface

chemistry and morphology of different mechanical pulps determined by ESCA and AFM,” Colloid Surface A. 228, 143-158.

Laine, J., Stenius, P., Carlsson, G., and Ström, G. (1994). “Surface characterization of unbleached kraft pulps by means of ESCA,” Cellulose 1, 145-160.

Lin, S. Y., and Dence, C. W. (1992). Methods in Lignin Chemistry, Springer Verlag, Berlin.

Lönnberg, B. (2009). “Idea of mechanical pulping,” Mechanical Pulping, Lönnberg, B., ed., Paperi ja Puu Oy, Helsinki.

Magaton, A. S., Colodette, J. L., Gouvêa, A. F. G., Gomide, J. L., Muguet, M. C. S., and Pedrazzi, C. (2009). Eucalyptus wood quality and its impact on kraft pulp production and use,” Tappi J. 8, 32-39.

Muguet, M. C. S., Pedrazzi, C., and Colodette, J. L. (2011). “Xylan deposition onto eucalypt pulp fibers during oxygen delignification,” Holzforschung 65, 605-612.

Musha, Y. and Goring, D. A. I. (1975). “Distribution of syringyl and guaiacyl moieties in hardwoods as indicated by ultraviolet microscopy,” Wood Sci. Tech. 9, 45-58.

Olsson, A.-M., and Salmén, L. (1997). “The effect of lignin composition on the viscoelastic properties of wood,” Nordic Pulp Pap. Res. J. 12, 140-145.

Pinto, P. C., Evtuguin, D. V., and Pascoal Neto, C. (2005). “Effect of structural features of wood biopolymers on hardwood pulping and bleaching performance,” Ind Eng Chem Res. 44, 9777-9784.

Prinsen, P., Gutiérrez, A., Rencoret, J., Nieto, L., Jiménez-Barbero, J., Burnet, A., Petit-Conil, M, Colodette, J. L., Martínez, A. T., and del Río, J. C. (2012). “Morphological characteristics and composition of lipophilic extractives and lignin in Brazilian woods from different eucalypt hybrids,” Ind. Crops and Prod. 36, 572-583.

Qiu, Z., Ni, Y., and Yang, S. (2003). “Using DTPA to decrease manganese-induced peroxide decomposition,” J. Wood. Chem. Tech. 23, 1-11.

Rencoret, J., Marques, G., Gutiérrez, A., Ibarra, D., Li, J., Gellerstedt, G., Santos, J. I., Jiménez-Barbero, J., Martínez, A. T., and del Río, J. C. (2008). “Structural characterisation of milled wood lignin from different eucalypt species,” Holzforschung 62, 514-526.

Rusu, M., Liukkonen, S., Gregersen, Ø., Sirviö, J. (2011). “The influence of fibre wall thickness and fibril angle on fibre development in the TMP process,” Nordic Pulp Pap J. 26, 6-13.

Santos, R. B., Capanema, E. W., Balakshin, M. Y., Chang, H.-M., and Jameel, H. (2011). “Effect of hardwoods characteristics on kraft pulping process: Emphasis on lignin structure,” BioResources 6, 3623-3637.

Scott, R. W. (1979). “Colorimetric determination of hexuronic acids in plant materials,” Anal. Chem. 7, 936-941.

Solar, R., Kacik, F., and Melcer, I. (1987). “Simple semimicro method for the determination of o-acetyl groups in wood and related materials,” Nordic Pulp Pap. Res. J. 4, 139-141.

Spence, K. L. (2011). “Processing and properties of microfibrillated cellulose,” Ph.D Thesis, North Carolina State University, Raleigh, United States of America.

Spence, K. L., Venditti, R. A., Rojas, O. J., Habibi, Y., and Pawlak, J. J. (2011). “A comparative study of energy consumption and physical properties of microfibrillated cellulose produced by different processing methods,” Cellulose 18, 1097-1111.

Stewart, J. J., Kadla, J. F. and Mansfield, S. D. (2006). “The influence of lignin chemistry and ultrastructure on the pulping efficiency of clonal aspen (Populus tremuloides Michx.),” Holzforschung 60, 111-122.

Tonoli, G. H. D., Savastano Jr., H., Fuente, E., Negro, C., Blanco, A., and Lahr, F. A. R. (2010). “Eucalyptus pulp fibers as alternative reinforcement to engineered cement-based composites,” Ind. Crop. Prod. 31, 225-232.

Thielemans, W., and Wool, R. P. (2005). “Kraft lignin as fiber treatment for natural fiber-reinforced composites,” Polym. Composite 26, 695-705.

Wallis, A. F. A., Wearne, R. H., and Wright, P. J. (1996). “Chemical analysis of polysaccharides in plantation eucalypt woods and pulps,” Appita J. 49, 258-262.

Watanabe, Y., Kojima, Y., Ona, T., Asada, T., Sano, Y., Fukazawa, K., and Funada, R. (2004). “Histochemical study on heterogeneity of lignin in Eucalyptus species II. The distribution of lignins and polyphenols in the walls of various cell types,” IAWA J. 25, 283-295.

Xu, E. C., and Sabourin, M. J. (1999). “Evaluation of APMP and BCTMP for market pulps from South American Eucalyptus,” Tappi J. 82, 75-82.

Xu, E. C., and Zhou, Y. (2007). “Synergistic effect between chemical mechanical pulps and chemical pulps from hardwoods,” Tappi J. 11, 4-9.

Zhou, Q., Baumann, M.J., Brumer, H., and Teeri, T. T. (2006). “The influence of surface chemical composition on the adsorption of xyloglucan to chemical and mechanical pulps,” Carbohyd Polym. 63, 449-458.

Article submitted: February 16, 2012; Peer review completed: June 23, 2012; Revised version received and accepted: June 29, 2012; Published: July 5, 2012; Figures 3 and 4 revised: June 17, 2013.