Accepted Manuscript

Title: Nanofibrillated cellulose (CNF) from eucalyptus

sawdust as a dry strength agent of unrefined eucalyptus
handsheets

Author: Marı́a Evangelina Vallejos Fernando Esteban Felissia

Marı́a Cristina Area Nanci Vanesa Ehman Quim Tarrés Pere
Mutjé

PII: S0144-8617(15)01182-0
DOI: http://dx.doi.org/doi:10.1016/j.carbpol.2015.12.004
Reference: CARP 10602

To appear in:

Received date: 24-9-2015

Revised date: 16-11-2015
Accepted date: 1-12-2015

Please cite this article as: Vallejos, M. E., Felissia, F. E., Area, M. C., Ehman, N. V.,
Tarrés, Q., and Mutjé, P.,Nanofibrillated cellulose (CNF) from eucalyptus sawdust as a
dry strength agent of unrefined eucalyptus handsheets, Carbohydrate Polymers (2015),
http://dx.doi.org/10.1016/j.carbpol.2015.12.004

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
Highlights (for review)

Highlights

Eucalyptus sawdust was fractionated to remove hemicelluloses (91%) and lignin (99%).

CNF was produced from the cellulosic fraction by TEMPO oxidation and homogenization.

The specific surface and diameter of CNF were 60 m2/g and 41.0 nm, respectively.

Tensile Index of handsheets increased 95% by addition of 9% CNF (27 to 55 Nm/g).

The increase in Tensile Index was equivalent to 1600 rpm of PFI refining.

t
ip
cr
us
an
M
e d
pt
ce
Ac

Page 1 of 35
*Manuscript

1 Nanofibrillated cellulose (CNF) from eucalyptus sawdust as a dry strength agent of

2 unrefined eucalyptus handsheets

4 María Evangelina Vallejos1,21*, Fernando Esteban Felissia1, María Cristina Area1,2,

5 Nanci Vanesa Ehman1,2, Quim Tarrés3 and Pere Mutjé3

t
ip
6

cr
7 Programa de Celulosa y Papel, Instituto de Materiales de Misiones, IMAM (UNaM-

8 CONICET). Félix de Azara 1552. Posadas, Misiones, Argentina.

us
9 *mariaxvallejos@gmail.com
2
10 Consejo Nacional de Investigación Científica (CONICET). Av. Rivadavia 1917,

11 CABA, Argentina
an
3
M
12 Grupo de investigación LEPAMAP. Departamento de Ingeniería Química, Universitat

13 de Girona. Campus Montilivi s/n 17071, Girona, España.

d

14
e

15 ABSTRACT
pt

16 Nanofibrillated cellulose has been obtained from the cellulosic fraction of eucalyptus

sawdust. The fractionation process involved the partial removal of hemicelluloses and
ce

17

18 lignin. CNF was obtained using TEMPO oxidation with NaOCl in basic medium
Ac

19 followed by mechanical homogenization. The obtained CNF was subsequently used as a

20 dry strength agent on unbleached unrefined eucalyptus pulp. The addition of 3, 6 and 9

21 wt. % of CNF increased lineally the tensile index of handsheets to about 55 N·m·g-1 at

22 35 °SR, compatible with papermachine runnability. The other mechanical properties

*
Corresponding author: María Evangelina Vallejos. Programa de Celulosa y Papel, Instituto de
Materiales de Misiones, IMAM (UNaM-CONICET). 1552 Félix de Azara St. ZIP Code 3300. Posadas,
Misiones, Argentina. Phone/Fax: +54-376-4422198, *mariaxvallejos@gmail.com

1
Page 2 of 35
23 also increased substantially, and porosity decreased moderately. The estimated specific

24 surface and average diameter of these CNF were 60 m2 g-1, and of 41.0 nm,

25 respectively. The addition of 9 wt. % of CNF produced an increase in mechanical

26 strength, equivalent to that produced by PFI refining at 1600 revolutions.

27

t
ip
28 KEYWORDS: biorefinery; eucalyptus sawdust; nanofibrillated cellulose;

cr
29 papermaking; surface addition; wet strength additive.

30

us
31 1. Introduction

32 Biomass is the main biopolymer source for sustainable and renewable uses in chemical,

33
an
material and fuel bio-products. The demand for bio-based products with equal or better
M
34 properties than conventional petroleum-based derived products has generated great

35 market opportunities. Nanotechnology is an emerging area of science and technology

d

36 that has revolutionized the field of materials. The application of nanotechnology will
e

37 exploit the potential of the forest and pulp and paper industries as a platform for bio-
pt

38 products.

The forest processing industry generates globally around 180 million of cubic metric of
ce

39

40 lignocellulosic residues (FAOSTAT, 2014) such as sawdust, bark and other wood
Ac

41 waste. The excess global sawdust potential after summit raw material demand of the

42 forest industry was estimated of 75 million of cubic metric. More than 67% of global

43 sawdust potential is located in Brazil, Canada and China (Heinimö, Pakarinen, Ojanen

44 & Kässi, 2007). Eucalyptus and pine sawdust are important byproducts of the primary

45 processing of wood in Argentina, Brazil and Chile which so far have not found a

46 successful exploitation. In some cases these residues represent a problem and its

2
Page 3 of 35
47 treatment consumes resources of management, treatment and disposal. In this context,

48 governments have established environmental regulations about its disposal in order to

49 promote their use and evaluate its potential as a renewable resource. Usually, sawdust is

50 used to obtain low value added products as pellets and briquettes (bioenergy), charcoal

51 (adsorbent), filler (composites) and wood panels (furniture and construction materials).

t
ip
52 An advantage of sawdust is that it does not require further mechanical treatment for size

cr
53 reduction. Its main disadvantage is the heterogeneity of the material, because sawmills

54 process woods from different origins, which generates a mixture of sawdust in which

us
55 species and age are difficult to know.

56 By chemical pulping processes, biomass is fractionated to obtain a pulp rich in

57
an
cellulose, lignin and other chemical components. This general principle can be used to
M
58 fractionate sawdust, separating all components by sequential processes, thus producing

59 high value products that can be used in different applications to improve the profit,
d

60 following the bio-refinery concept. Although sawdust has been tested to make pulp for
e

61 paper, product quality is not good. However, the possibility of producing CNF with this
pt

62 resource appears as an excellent chance of valorization of this waste. In this form, wood

can be fully exploited and traditional pulping can be combined with new technologies,
ce

63

64 conversion infrastructure, and technical knowhow, to develop new bio-based and high
Ac

65 value added products.

66 The autohydrolysis of lignocellulosic materials in aqueous medium at elevated

67 temperature in a pressure reactor is one of the most effective treatments for

68 hemicelluloses solubilization (Garrote, Eugenio, Díaz, Ariza & López, 2003; Sasaki,

69 Adschiri & Arai, 2003). The partial solubilization of hemicelluloses (70-90%) to

70 oligosaccharides and monosaccharides takes place, which can be used for different

3
Page 4 of 35
71 purposes (Teramoto, Tanaka, Lee & Endo, 2008). Hardwood and grass species are more

72 suitable for the autohydrolysis treatment than conifers, due to their higher content of

73 acetyl groups which provide an increase of catalyst concentration in the reaction

74 medium. On the other hand, lignin can be removed by alternative pulping processes

75 such as kraft, soda-anthraquinone or organosolv pulping to obtain sulfur-free lignin.

t
ip
76 The use of the cellulosic fraction to produce micro and nanofibrillated cellulose (MFC

cr
77 or CNF, respectively) grew strongly in recent years due to their unique properties,

78 renewable nature and large availability. CNF and MFC are fibrils or aggregates of

us
79 cellulose with a diameter between 5 and 60 nm and several microns in length. CNF is

80 obtained from the delamination of the cellulosic fibers by mechanical treatment of

81
an
chemical or enzymatically pretreated fibers (González, Boufi, Pèlach, Alcalà, Vilaseca
M
82 & Mutjé, 2012). The processes used affect the structure, properties, and price of CNFs,

83 therefore the great challenge of research studies is to find a process to produce large
d

84 amounts of cellulose nanofibers at low-cost (low amount of energy, inexpensive

e

85 reagents and efficient enzymes). This process should keep the properties of cellulose
pt

86 and generate nanofibers with uniform size distribution (length and diameter). CNF is

produced by pumping the pretreated fiber slurry (consistency 1 - 2%) in a high pressure
ce

87

88 homogenizer where the fibers are forced to collide with a valve andan impact ring. This
Ac

89 procedure generates shear forces and a pressure drop, causing fiber delamination and

90 the release of the microfibrils from the fiber wall layers. The fibrous slurry acquires the

91 appearance and characteristics of a gel after several passes through the homogenizer.

92 Micro-fibrillation may be facilitated by TEMPO oxidation in water (Nakagaito & Yano,

93 2004), which consists of a selective surface catalytic oxidation of the primary hydroxyls

94 of cellulose at the C6 position to carboxylate groups by 2,2,6,6-tetramethylpiperidine-1-

4
Page 5 of 35
 95 oxyl (TEMPO) (Saito & Isogai, 2004; Saito, Kimura, Nishiyama & Isogai, 2007; Saito,

96 Nishiyama, Putaux, Vignon & Isogai, 2006). This chemical pretreatment is effective in

97 the cellulose oxidation and also reduces the energy consumption in the subsequent

98 mechanical processing for MFC and CNF production. Recently, this methodology has

99 been used to facilitate the mechanical treatment of cellulosic fibers (Isogai, 2013;

t
ip
100 Isogai, Saito & Fukuzumi, 2011; Puangsin, Yang, Saito & Isogai, 2013).

cr
101 Since the advent of nanotechnology, CNF has been used for nanopaper manufacture and

102 many authors have also studied the effect of nanoparticles (mostly, MFC) on

us
103 conventional paper. CNF applied directly in the paper sheet showed the enhancement of

104 the mechanical strength and the improvement of the filler retention in the wet-end. This

105
an
was attributed to the increment of the number of hydrogen bonds fibril-fibers (Kajanto
M
106 & Kosonen, 2012). Similar to cellulosic fines, CNF increases the network strength due

107 to its high surface area and flexibility. CNF has several advantages as reinforcing
d

108 element: small diameter, high aspect ratio, biocompatibility, functionalization ability,
e

109 and high strength and modulus. These characteristics become attractive to CNF as dry
pt

110 strength additive for paper. The use of CNF as reinforcement improves the permeability

and tensile index of papers (Eriksen, 2008; González, Boufi, Pèlach, Alcalà, Vilaseca &
ce

111

112 Mutjé, 2012; Mörseburg & Chinga-Carrasco, 2009; Nakagaito & Yano, 2004; Taipale,
Ac

113 Österberg, Nykänen, Ruokolainen & Laine, 2010). The increase of paper strength with

114 CNF addition can be compared with strength gain after a slight refining (González,

115 Boufi, Pèlach, Alcalà, Vilaseca & Mutjé, 2012). Also it has been shown that CNF

116 addition increases the strength of canola waste chemithermomechanical pulp in fluting

117 and linerboard manufacture for packing papers (González, Alcalá, Arbat, Vilaseca &

118 Mutjè, 2013).The addition of CNF to an unrefined pulp produce handsheets with higher

5
Page 6 of 35
119 tensile strength than standard handsheets (Bardet & Bras, 2014) allowing significant

120 reduction of grammage and energy saving (refining or drying process). Nevertheless,

121 CNF have different chemical natures and morphologies depending on the source and

122 process, so results are variable (Bardet & Bras, 2014). However, the addition of CNF as

123 dry strength additive in the papermaking furnish decreases the drainage capacity of the

t
ip
124 slurry (González, Alcalà, Chinga-Carrasco, Vilaseca, Boufi & Mutjé, 2014; González,

cr
125 Boufi, Pèlach, Alcalà, Vilaseca & Mutjé, 2012), limiting the amount of CNF that could

126 be added.

us
127 The aim of this study was to evaluate the effect of the addition of CNF obtained from

128 the cellulosic fraction of eucalyptus sawdust on the mechanical properties of paper

129 made from unrefined unbleached eucalyptus pulp.

an
M
130

131 2. Material and Methods

d

132 2.1 Materials

e

133 CNF was obtained from sawdust generated in a sawmill (Candela Sawmill, Misiones,
pt

134 Argentina) which proceeds from a mixture of eucalyptus species (E. grandis, E. saligina

y E. rostrata from).
ce

135

136 Unbleached eucalyptus pulps, cationic starch and colloidal silica were provided by
Ac

137 Montañanesa Group Torraspapel, Zaragoza, Spain.

138

139 2.2 Eucalyptus sawdust fractionation and purification of the cellulosic fraction

140 Eucalyptus sawdust was fractionated applying biorefinery concept by sequential

141 extraction of hemicelluloses and lignin separately for further applications and cellulosic

142 fraction was purified by oxygen delignification before using it as raw material to obtain

6
Page 7 of 35
143 CNF (Figure 1).

144

145 Figure 1

146

147 The sawdust was classified and the fraction passing 18 mesh and retained on 80 mesh

t
ip
148 was sequentially fractionated by autohydrolysis to remove the hemicelluloses and

cr
149 delignification treatments. The autohydrolysis stage was accomplished using a 4.5 L

150 digester with a heating jacket and a special agitation system and 450 g of eucalyptus

us
151 sawdust. The considered factors were: time 20 min, temperature 180°C, and liquid/solid

152 ratio of 6.

153
an
The residual solid of the autohydrolysis was sequentially subjected to two delignifying
M
154 treatments: (i) alkaline soda-anthraquinone and (ii) oxygen, to extract residual lignin.

155 The soda-AQ stage was carried out using 20% of NaOH, 0.1% of AQ (wt. %, dry basis
d

156 of residual solid) at 170 °C for 30 min and a liquid/solid ratio of 5.70. Oxygen
e

157 delignification was conducted in a multipurpose reactor, equipped with a high shear
pt

158 rotor which generates the required agitation conditions in the system, an inlet for

oxygen and a heating system. The material was treated with a 3% NaOH charge (o.d.),
ce

159

160 0.1% MgSO4 (o.d.) at 10% consistency. The operational conditions were 100 °C for 60
Ac

161 min and an oxygen pressure of 6 kg cm-2 (more details in reference (Rodríguez Rivero,

162 Ehman, Area & Felissia, 2013).

163

164 2.3 Chemical characterization of the raw material and the solid fraction

165 The chemical characterization of eucalyptus sawdust before and after fractionation was

166 performed according to laboratory analytical procedures (LAPs) for standard biomass

7
Page 8 of 35
167 analysis from the National Renewable Energy Laboratory (NREL). Carbohydrates,

168 organic acids and other products (furfural, HMF) were identified by liquid

169 chromatography (HPLC) using an Aminex-HPX87H (Bio-Rad) column with refractive

170 index and diode array detectors. The soluble lignin was determined by UV-visible

171 spectrophotometry at 205 nm according to TAPPI UM 250 “Acid-soluble lignin in

t
ip
172 wood and pulp”. The polymeric carbohydrates were hydrolyzed to monomers and

cr
173 quantified by HPLC. The monomer concentrations were multiplied by the following

174 conversion factors to be expressed as polymers: glucose to glucans: 0.900, HMF to

us
175 glucans: 1.286, xylose to xylans: 0.880, furfural to xylans: 1,375, arabinose to

176 arabinans: 0.880 and acetic acid to acetyl: 0.717.

177
an
The viscosity of the cellulosic materials was determined according to ISO 5351-1

“Cellulose in dilute solutions - Determination of limiting viscosity number - Part 1:

M
178

179 Method in cupri-ethylenediamine (CED) solution”. Carboxyl groups were determined

d

180 by conductimetric titration. The cellulosic fractions were first washed with 0.1 N HCl
e

181 for 45 minutes and after they were washed with distilled water until a conductivity value
pt

182 close to distilled water. The washed materials (1-3 g of dry material) were suspended in

a solution of 0.1 M of HCl with stirring. The slurries were titrated with a solution of 0.1
ce

183

184 M of NaHCO3 and the conductivity was recorded in mS cm-1 until stabilization and
Ac

185 subsequent increase of conductivity.

186

187 2.4 CNF preparation

188 The oxidation of the cellulosic fraction was performed with 2,2,6,6-

189 tetramethylpiperidine-1-oxyl (TEMPO), sodium bromide and a commercial solution of

190 sodium hypochlorite. TEMPO oxidation was carried out on 15 g of dry cellulosic

8
Page 9 of 35
191 fraction of sawdust (previously disintegrated). The cellulosic fraction was suspended in

192 1000 mL of distilled water containing 0.016 g of TEMPO g-1 of dry material and 0.1 g

193 of NaBr g-1 of dry material. The TEMPO oxidation was performed at room temperature

194 using 6 mmol of NaClO g-1 of dry material (solution 15 wt. %). The solution of NaClO

195 was added dropwise with stirring, so that pH was maintained at 10. After NaClO

t
ip
196 addition, a solution of 0.5 M of NaOH was added dropwise until pH did not decrease

cr
197 below 10. The TEMPO oxidized cellulosic fraction was washed with distilled water

198 until neutral pH and filtered. CNF was obtained by mechanical treatment of the oxidized

us
199 cellulosic fraction slurry (1% consistency) in a Panda homogenizer (GEA Niro Soavi).

200 A total of 5 passes at 300 bar and 10 passes at 600 bar through the homogenizer were

201 required to obtain a gel characteristic.

an
M
202

203 2.5 CNF characterization

d

204 To measure cationic demand (Mütek PCD 04), the CNF (0.04 g) was diluted in 1000
e

205 mL of distilled water and dispersed in a disintegrator for 10 min at 3000 rpm. This
pt

206 slurry (10 mL) was mixed with 25 mL of the cationic polymer polyDADMAC

(polydiallyldimethylammonium chloride) for 5 min with magnetic stirring. The mixture

ce

207

208 was centrifuged for 90 min at 4000 rpm, and the supernatant (10 mL) was titrated in the
Ac

209 particle charge detector with the anionic polymer PES-Na added dropwise until 0 mV.

210 The consumed volume of the anionic polymer was used to calculate the cationic

211 demand of CNF.

212 To measure conversion yields of fibers to CNF, the homogenized slurry (consistency

213 0.1%) was centrifuged for 20 min at 10000 rpm. The supernatant (with the CNF) was

214 separated from the solid fraction (partially fibrillated fibers) and it was dried at 105 °C

9
Page 10 of 35
215 for 24 hours. Yield was determined as the percentage of the dry weight of CNF in the

216 supernatant relative to the dry weight of the fibrous material in the initial slurry.

217 The polymerization degree (DP) was calculated from intrinsic viscosity by Equations

218 (1) and (2) (Marx-Figini, 1987).

219

t
ip
220 (1)

cr
221 (2)

us
222

223 Where, ηs is the intrinsic viscosity of the cellulosic material, determined by the ISO

224
an
standard 5351-1: “Determination of limiting viscosity number in cupri-ethylenediamine

225 (CED) solution”.

M
226 The water retention value (WRV) of the CNF was performed on two fractions of the

227 same weight of CNF gel, centrifuged at 2400 rpm for 30 min to remove unbound water.
d

228 Nitrocellulose membranes were placed at the bottom of the centrifuge containers (pore
e

diameter of 0.65 ) to retain the CNF. The samples were dried at 105 °C for 24 h to
pt

229

230 determine the dry weight. WRV was calculated as the percentage of the weight of
ce

231 retained water respect to the dry weight of CNF (methodology based on TAPPI UM

232 256).
Ac

233 CNF mean diameter was determined from its specific surface. The specific surface of

234 CNF was calculated from the difference between its cationic demand and the carboxyl

235 group content. This difference corresponds to the cationic polymer unabsorbed by the

236 carboxyl groups (Mutjé, 1989). This value was multiplied by the specific surface

237 generated per 1 micro-equivalent of poly-DADMAC cationic polymer (1.027·1017 nm2)

238 to obtain the specific surface of 1 g of CNF. Finally, the diameter of CNF was

10
Page 11 of 35
239 calculated by Eq. (2):

240

241 (2)

242

t
243 Where, is the specific surface of CNF, ρ is the density of the cellulose (1.53 g

ip
244 m2) and d is the diameter of the CNF.

cr
245

us
246 2.6 Addition of sawdust CNF and sheet formation

247 Unbleached eucalyptus pulp together with CNF was dispersed using a laboratory

248

249
an
disintegrator at 3000 rpm for 60 min. The amounts of each component were calculated

to obtain handsheets of 75 g m-2, with 0, 3, 6, and 9 wt. % of CNF. Then, cationic starch
M
250 and colloidal silica (0.5 to 0.8 wt. % on dry basis of pulp, respectively) were added and

251 the slurry was stirred mechanically for 20 minutes. The handsheets were formed in a
d

252 Rapid Köthen type laboratory sheet former (ISP mod. 786FH) according to ISO 5269-2.
e

253 Handsheets drying was carried out at 80°C in the vacuum dryer equipment incorporated
pt

254 in the sheet former. After recording the weight of the handsheets, they were conditioned
ce

255 in a conditioned chamber at 25 °C and 50% RH. To form handsheets from refined

256 pulps, a slurry of 10% consistency was refined in a PFI laboratory refiner (NPFI 02
Ac

257 Metrotec SA) at 1000, 2000 and 3000 revolutions, and then the above described

258 procedure was followed.

259

260 2.7 Properties of handsheets

261 Pulps drainage was measured with a Schopper-Riegler equipment (mod. 95587 PTI)

262 following the ISO 5267/1 standard. The pulp fiber length distribution was determined

11
Page 12 of 35
263 on a pulp suspension of 0.025% consistency, using a MorFi Compact analyzer

264 (TechPap). The results were acquired and analyzed with the MORFI v.8.3 software.

265 Tensile index was performed with a universal testing machine equipped with a

266 Hounsfield 42 (load cell of 2.5 kN) following the ISO 1924-1 and 1924-2 standards.

267 Burst index was determined by a IDM mod. EM-50 equipment (ISO 2758 standard).

t
ip
268 Density was calculated from the weight and dimensions of handsheets, whereas porosity

cr
269 was calculated using Eq. (3):

270

us
271 (3)

272

273 Where, handsheets

an
is the density of the handsheets and cellulose is the density of cellulose
M
274 (1.53 g cm-3).

275
d

276 3. Results and Discussion

e

277
pt

278 3.1 CNF manufacture and properties

ce

279 Chemical composition of eucalyptus sawdust (total on od wood) was: 41.8% of glucans,

280 10.7 % of xylans, 1.41% of acetyl groups, 32.3% of lignin, 7.86% of extractives and
Ac

281 0.59% of ashes.

282 Autohydrolysis yield was 82.2% and the total extracted hemicelluloses respect to initial

283 content was 80.0% (8.53% total on od wood). Carbohydrate content in the residual

284 liquor expressed as percentages of total wood was 9.74% (2.93% of xylose, 0.20% of

285 arabinose, 0.83% of glucans, 5.76% of xylans and 0.02% of arabinans) and acetyl

286 groups content was 0.65%. The main degradation products in residual liquors were

12
Page 13 of 35
287 acetic acid (0.74%), formic acid (0.18%), furfural (0.12%) and HMF (0.01%).

288 Kappa number of the cellulosic fraction of sawdust from the hydrothermal- alkaline

289 soda-anthraquinone treatment was 19.4. After the oxygen stage the cellulosic fraction

290 reached 70.1% delignification, Kappa number dropped from 19.4 to 5.8, intrinsic

291 viscosity was 598 mL g-1 (degree of polymerization 1513), and hemicelluloses content

t
ip
292 was lower 3% on over dry cellulosic fraction (global yield: 30.8%).

cr
293 The characteristics of the CNF are shown in Table 1.

294

us
295 Table 1

296

297
an
The carboxyl group content of sawdust highly increased after oxidation (from of 24.3 to
M
298 370.6 μeq-g g-1 COO-), which contributed to the next homogenization stage. The

299 obtained cationic demand of 495 μeq-g g-1 showed that a portion of poly-DADMAC has
d

300 been ion exchanged while the remaining has been adsorbed by London - Van der Waals
e

301 forces, therefore, assuming that the polymer has been adsorbed as a monolayer this
pt

302 amount should be proportional to the surface area of the CNF, which was 60.6 m2 g-1
ce

303 (Mutjé, 1989). Accordingly, assuming that the CNF particles are ideally cylindrical, the

304 mean diameter would be 41 nm. As the elementary fibril has a diameter of 3 to 5 nm,
Ac

305 the obtained value indicates a wide range of diameters, evidencing the presence of

306 elementary CNF as well as bundled CNF. This result is consistent with the

307 homogenization yield (60% approximately). The diameters of CNF were verified by

308 FE-SEM microphotography, as reflected in Figure 2.

309

310 Figure 2.

13
Page 14 of 35
311

312 Finally, a strong depolymerization of cellulose was evidenced by the polymerization

313 degree, which decreased from 1513 in the fractioned sawdust to 203 in the CNF,

314 affecting its intrinsic properties. As sawdust cellulosic fraction has low hemicellulose

315 content (< 3%) is expected that affect its performance as dry strength additive when

t
ip
316 added in the papermaking furnish. The hemicelluloses are distributed between cellulose

cr
317 microfibrils allowing an easy penetration of TEMPO molecules during oxidation

318 (Isogai, 2013) and facilitating the nanofibrillation of cellulosic fraction (Chaker, Alila,

us
319 Mutjé, Vilar & Boufi, 2013). Pulps with the higher hemicellulose content reach higher

320 yields of the nanofibrillated fraction and a better aptitude for microfibrils

321
an
individualization (Alila, Besbes, Vilar, Mutjé & Boufi, 2013; Chaker, Alila, Mutjé,
M
322 Vilar & Boufi, 2013; Galland, Berthold, Prakobna & Berglund, 2015). By comparison,

323 CNF obtained from bleached eucalyptus fibers has a theoretical specific surface area of
d

324 240.1 m2 g-1, an average diameter of 10.4 nm, and a polymerization degree of 352 at the
e

325 same oxidation level (González, Alcalá, Arbat, Vilaseca & Mutjè, 2013; González,
pt

326 Boufi, Pèlach, Alcalà, Vilaseca & Mutjé, 2012). Bleached kraft pulp generally contain

around 5–15% of hemicelluloses which may have favored the nanofibrillation. Figure 3
ce

327

328 shows CNFs obtained from TEMPO-oxidized sawdust cellulosic fraction.

Ac

329

330 Figure 3.

331

332 3.2 Unbleached eucalyptus pulp refining

333 The fiber length distribution of the unrefined unbleached eucalyptus pulp is shown in

334 Figure 4.

14
Page 15 of 35
335

336 Figure 4

337

338 The length weighted in length and fiber diameter of the eucalyptus unrefined

339 unbleached pulp were 557 μm and 16.7 μm, respectively with a fine content of 15.6%.

t
ip
340 The properties of this pulp were 16°SR (Schopper – Riegler degree), kappa index 14

and 27.3 N·m·g-1 of tensile index. The fraction of particles smaller than 76 microns

cr
341

342 were considered fines, so fiber length weighted in length was smaller than the usual

us
343 values for this pulps. On the contrary, °SR, Kappa number and tensile index values were

344 the usual for this kind of never-dried pulp (Area, Carvalho, Ferreira, Felissia, Barboza

345
an
& Bengoechea, 2010). The variation of handsheets properties from this pulp with the
M
346 refining treatment are shown in Table 2.

347
d

348 Table 2
e

349
pt

350 PFI refining produces internal and external fibrillation and a consequently, the swelling

capacity of fibers increases (Carrasco, Mutjé & Pèlach, 1996). Other consequences are
ce

351

352 the reduction of fiber length, the increase of fines percentage and the decrease of
Ac

353 drainage capacity. As shown in Table 2, this treatment increased density and strength,

354 whereas drainage and porosity decreased. In the studied interval, °SR increased linearly,

355 certainly due to the increase in specific surface of fibers, and mechanical tensile

356 properties improved correspondingly. The increase of applied energy (number of

357 revolutions) produced an almost linear evolution of tensile index, which correspond to

358 other physical and mechanical properties of the paper as Scott bond and burst index.

15
Page 16 of 35
359 Refining also increased Young's modulus of the paper (rigidity) and density (reduced

360 bulk) so the percentage of paper voids (porosity) decreases linearly. Industrial refining

361 produces greater effects than laboratory refining in PFI, especially of morphological

362 type, since the industrial disc refiner enhances fiber fibrillation and cutting, increasing

363 fines percentage and decreasing fiber length.

t
ip
364

cr
365 3.3 CNF addition as papermaking additive

366 Handsheets properties of an unbleached unrefined pulp with different charges of CNF

us
367 from the cellulosic fraction of eucalyptus sawdust are shown in Table 3.

368

369 Table 3
an
M
370

371 The addition of 9 wt. % of CNF to this cellulosic fraction of sawdust produced a lineal
d

372 increase in mechanical strength, equivalent to that produced by 1600 revolutions of PFI
e

373 refining (53.3 N·m·g-1). However, the incorporation of the same percentage of CNF
pt

374 produced from eucalyptus bleached pulp to the same furnish generated a tensile index

46% higher, equivalent to 3500 revolutions of PFI refining (González, Alcalà, Chinga-
ce

375

376 Carrasco, Vilaseca, Boufi & Mutjé, 2014; González, Boufi, Pèlach, Alcalà, Vilaseca &
Ac

377 Mutjé, 2012). Although the improvement in properties produced by adding CNF from

378 the cellulosic fraction of sawdust was a bit inferior, its effect on Young Module was in

379 the same order to those obtained when unbleached eucalyptus pulp was refiner at

380 different revolutions. The Young Module of handsheets with 9 wt. % of CNF from

381 eucalyptus bleached pulp was equivalent to Young Module of handsheets refined at

382 3000 revolutions. Similarly, °SR increase was low when sawdust CNF was added (34

16
Page 17 of 35
383 ºSR vs. 68 ºSR with the addition of 9 wt. % CNF from eucalyptus bleached pulp). WRV

384 showed analogous behavior (5.1 g H2O·g-1 vs. 8.3 g H2O·g-1). Density, burst index and

385 porosity also reflected the lower bonding capacity of CNF from the cellulosic fraction

386 of sawdust. On the contrary, Young's modulus (stiffness) showed the similar values than

387 those obtained by refining at 3000 revolutions. Tensile strength of the paper is

t
ip
388 controlled by the tensile strength of fibers and by the strength of interfiber bonding. As

well, the strength of interfiber bonding depends on the relative bonded area “RBA”

cr
389

390 between fibers, and of the bond strength per unit of bonded area “b”(Page, 1969). For

us
391 the same fiber strength, CNF addition would act as an adhesive increasing “RBA” and

392 “b”, thus increasing the tensile strength of the sheet. The same behavior is usually

393
an
verified for burst strength. This is also reflected by density, which increased to 0.695

g·cm-3 (5%) and porosity, which decreased up to 53.65%. This can be interpreted as a
M
394

395 positive effect on barrier properties. Figure 5 shows SEM images of handsheets (60
d

396 g·m-2) of unbleached unrefined pulp (Figure 5.a and 5.c) and of the unbleached
e

397 unrefined pulp with 6 wt. % of CNF from the cellulosic fraction of eucalyptus sawdust
pt

398 (Figure 5.b and 5.d).

ce

399

400 Figure 5.
Ac

401

402 Other groups reported similar results using comparable systems. Addition of 10% CNF

403 (prepared from bleached softwood sulphite pulp) to unrefined softwood sulphite pulp

404 without retention aid, produced similar improvement on tensile strength and density of

405 handsheets than pulp refining (Sehaqui, Zhou & Berglund, 2013). Increased density and

406 strength are reported in studies where CNF was added to sheets (Ahola, Österberg &

17
Page 18 of 35
407 Laine, 2008; Eriksen, 2008; Sehaqui, Zhou & Berglund, 2013). Possible reasons are: (i)

408 CNF is fine material which helps to consolidate the sheet, and (ii) CNF is attached to

409 fiber surfaces as a layer, thus increasing the number of hydrogen bonds (Brodin,

410 Gregersen & Syverud, 2014).

411

t
ip
412 4. Conclusions

cr
413 CNF (virtually free of hemicelluloses and lignin) was obtained from an eucalyptus

414 sawdust cellulosic fraction using a sequential processes into a biorefinery concept. The

us
415 production of CNF from sawdust cellulosic fraction achieved 60% yield. The lower

416 yield of the nanofibrillated fraction can be attributed to low hemicelluloses content in

417
an
the cellulosic fraction. The estimated specific surface and average diameter of these

CNF were 60 m2g-1, and 41.0 nm, respectively.

M
418

419 The addition of 9% of CNF to an unbleached unrefined pulp produced a lineal increase
d

420 in mechanical strength, equivalent to that produced by 1600 revolutions PFI refining.
e

421
pt

422 References

Ahola, S., Österberg, M., & Laine, J. (2008). Cellulose nanofibrils – adsorption with
ce

423

424 poly(amideamine) epichlorohydrin studied by QCM-D and application as a paper

Ac

425 strength additive. Cellulose, 15(2), 303-314.

426 Alila, S., Besbes, I., Vilar, M. R., Mutjé, P., & Boufi, S. (2013). Non-woody plants as

427 raw materials for production of microfibrillated cellulose (MFC): A comparative

428 study. Industrial Crops and Products, 41, 250-259.

429 Area, M. C., Carvalho, M. G. V. S., Ferreira, P. J., Felissia, F. E., Barboza, O. M., &

430 Bengoechea, D. I. (2010). The influence of pulping and washing conditions on the

18
Page 19 of 35
431 properties of Eucalyptus grandis unbleached kraft pulps treated with chelants.

432 Bioresource Technology, 101(6), 1877-1884.

433 Bardet, R., & Bras, J. (2014). Cellulose Nanofibers and Their Use in Paper Industry.

434 Handbook of Green Materials (pp. 207-232).

435 Brodin, F. W., Gregersen, Ø. W., & Syverud, K. (2014). Cellulose nanofibrils:

t
ip
436 Challenges and possibilities as a paper additive or coating material – A review.

cr
437 Nordic Pulp & Paper Research Journal, 29 (1), 156-166.

438 Carrasco, F., Mutjé, P., & Pèlach, M. A. (1996). Refining of bleached cellulosic pulps:

us
439 characterization by application of the colloidal titration technique. Wood Science

440 and Technology, 30(4), 227-236.

441
an
Chaker, A., Alila, S., Mutjé, P., Vilar, M., & Boufi, S. (2013). Key role of the
M
442 hemicellulose content and the cell morphology on the nanofibrillation effectiveness

443 of cellulose pulps. Cellulose, 20(6), 2863-2875.

d

444 Eriksen, O. (2008). The use of microfibrillated cellulose produced from kraft pulp as
e

445 strength enhancer in TMP paper. Nordic Pulp and Paper, 23(3), 299-304.
pt

446 FAOSTAT. (2014). Forest Products (2008-2012). FAO Statistics Series (Vol. 47, p.

358). Roma: Food and Agriculture Organization of the United Nations (FAO).
ce

447

448 Galland, S., Berthold, F., Prakobna, K., & Berglund, L. A. (2015). Holocellulose
Ac

449 Nanofibers of High Molar Mass and Small Diameter for High-Strength Nanopaper.

450 Biomacromolecules, 16(8), 2427-2435.

451 Garrote, G., Eugenio, M. E., Díaz, M. J., Ariza, J., & López, F. (2003). Hydrothermal

452 and pulp processing of Eucalyptus. Bioresource Technology, 88(1), 61-68.

453 González, I., Alcalá, M., Arbat, G., Vilaseca, F., & Mutjè, P. (2013). Suitability of

454 Rapeseed Chemithermomechanical Pulp as Raw Material in Papermaking.

19
Page 20 of 35
455 González, I., Alcalà, M., Chinga-Carrasco, G., Vilaseca, F., Boufi, S., & Mutjé, P.

456 (2014). From paper to nanopaper: evolution of mechanical and physical properties.

457 Cellulose, 21(4), 2599-2609.

458 González, I., Boufi, S., Pèlach, M. A., Alcalà, M., Vilaseca, F., & Mutjé, P. (2012).

459 Nanofibrillated cellulose as paper additive in eucalyptus pulps. BioResources, 7(4),

t
ip
460 5167- 5180.

cr
461 Heinimö, J., Pakarinen, V., Ojanen, V., & Kässi, T. (2007). International bioenergy

462 trade - scenario study on international biomass market in 2020. (p. 54): Department

us
463 of Industrial Engineering and Management, Lappeenranta University of

464 Technology.

465
an
Isogai, A. (2013). Wood nanocelluloses: fundamentals and applications as new bio-
M
466 based nanomaterials. Journal of Wood Science, 59(6), 449-459.

467 Isogai, A., Saito, T., & Fukuzumi, H. (2011). TEMPO-oxidized cellulose nanofibers.
d

468 Nanoscale, 3(1), 71-85.

e

469 Kajanto, I., & Kosonen, M. (2012). The potential use of micro- and nanofibrillated
pt

470 cellulose as a reinforcing element in paper. Journal of Science & Technology for

Forest Products and Processes, 2(6), 42-48.

ce

471

472 Marx-Figini, M. (1987). The acid-catalyzed degradation of cellulose linters in distinct

Ac

473 ranges of degree of polymerization. Journal of Applied Polymer Science, 33(6),

474 2097-2105.

475 Mörseburg, K., & Chinga-Carrasco, G. (2009). Assessing the combined benefits of clay

476 and nanofibrillated cellulose in layered TMP-based sheets. Cellulose, 16(5), 795-

477 806.

478 Mutjé, P. (1989). Contribución al estudio de la retención de finos y cargas en la

20
Page 21 of 35
479 fabricación del papel. Escuela Técnica Superior de Ingenieros Industriales de

480 Terrassa, Universitat Politècnica de Catalunya (Vol. Doctoral Thesis).

481 Nakagaito, A. N., & Yano, H. (2004). The effect of morphological changes from pulp

482 fiber towards nano-scale fibrillated cellulose on the mechanical properties of high-

483 strength plant fiber based composites. Applied Physics A, 78(4), 547-552.

t
ip
484 Page, D. H. (1969). A theory for the tensile strength of paper. Tappi Journal, 52(4),

cr
485 674-681.

486 Puangsin, B., Yang, Q., Saito, T., & Isogai, A. (2013). Comparative characterization of

us
487 TEMPO-oxidized cellulose nanofibril films prepared from non-wood resources.

488 International Journal of Biological Macromolecules, 59, 208-213.

489
an
Rodríguez Rivero, G. E., Ehman, N. V., Area, M. C., & Felissia, F. E. (2013).
M
490 Purification of the cellulosic fraction from the fractionation of Eucalyptus sp.

491 sawdust by oxidative treatments. 6th International Colloquium on Eucalyptus Pulp

d

492 Colonia del Sacramento, Uruguay.

e

493 Saito, T., & Isogai, A. (2004). TEMPO-Mediated Oxidation of Native Cellulose. The
pt

494 Effect of Oxidation Conditions on Chemical and Crystal Structures of the Water-

Insoluble Fractions. Biomacromolecules, 5(5), 1983-1989.

ce

495

496 Saito, T., Kimura, S., Nishiyama, Y., & Isogai, A. (2007). Cellulose nanofibers prepared
Ac

497 by TEMPO-mediated oxidation of native cellulose. Biomacromolecules, 8(8),

498 2485–2491.

499 Saito, T., Nishiyama, Y., Putaux, J. L., Vignon, M., & Isogai, A. (2006). Homogeneous

500 suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of

501 native cellulose. Biomacromolecules, 7(6), 1687–1691.

502 Sasaki, M., Adschiri, T., & Arai, K. (2003). Fractionation of sugarcane bagasse by

21
Page 22 of 35
503 hydrothermal treatment. Bioresource Technology, 86(3), 301-304.

504 Sehaqui, H., Zhou, Q., & Berglund, L. A. (2013). Nanofibrillated cellulose for

505 enhancement of strength in high-density paper structures. Nordic Pulp & Paper

506 Research Journal, 28(2), 182-189.

507 Taipale, T., Österberg, M., Nykänen, A., Ruokolainen, J., & Laine, J. (2010). Effect of

t
ip
508 microfibrillated cellulose and fines on the drainage of kraft pulp suspension and

cr
509 paper strength. Cellulose, 17(5), 1005-1020.

510 Teramoto, Y., Tanaka, N., Lee, S.-H., & Endo, T. (2008). Pretreatment of eucalyptus

us
511 wood chips for enzymatic saccharification using combined sulfuric acid-free

512 ethanol cooking and ball milling. Biotechnology and Bioengineering, 99(1), 75-85.

513
an
M
514
e d
pt
ce
Ac

22
Page 23 of 35
515 ACKNOWLEDGMENTS

516 The authors acknowledge of the Value-Added Products from Forest and Agroindustrial

517 Residues Network (PROVALOR-CYTED) for the financial support.

518

t
ip
cr
us
an
M
e d
pt
ce
Ac

23
Page 24 of 35
519 FIGURE CAPTIONS

520

521 Figure 1. Schematic process used to obtain nanofibrillated cellulose from

522 eucalyptus sawdust applying the biorefinery concept.

523

t
ip
524 Figure 2. Diameters of CNFs by FE-SEM microphotography.

cr
525

526 Figure 3. CNFs from the TEMPO-oxidized cellulosic fraction of eucalyptus

us
527 sawdust.

528

529
an
Figure 4. Fiber length distribution of the unrefined unbleached eucalyptus pulp.
M
530

531 Figure 5. SEM images of a 60 g m-2 handsheets of (a and c) an unbleached

d

532 unrefined pulp, (b and d) the same pulp with 6 wt. % of CNF.
e

533
pt
ce
Ac

24
Page 25 of 35
534 TABLE CAPTIONS

535

536 Table 1. Properties of CNF.

537

538 Table 2. Properties of the refined unbleached eucalyptus pulp.

t
ip
539

cr
540 Table 3. Effect of CNF from cellulosic fraction of eucalyptus sawdust addition on

541 the properties of unbleached unrefined pulp.

us
542
543
an
M
e d
pt
ce
Ac

25
Page 26 of 35
Table(s)

Table 1. Characterization of the obtained CNF.

Nanofibrillation yield 60% (approximately)

Initial carboxyl groups content 24.3 μeq-g g-1 COO-
Pos-oxidation carboxyl groups content 370.6 μeq-g g-1 COO-
Cationic demand 495 μeq-g g-1 poly-DADMAC
Water retention value 5.1 g H2O g-1

t
Polymerization degree 203

ip
Specific surface of CNF 60.6 m2 g-1
Diameter of CNF 41 nm

cr
us
an
M
e d
pt
ce
Ac

Page 27 of 35
Table(s)

Table 2. Properties of the refined unbleached eucalyptus pulp (± standard

deviation).

Rev. Tensile index E Density Burst Index Porosity

ºSR
PFI (N·m·g-1) (GPa) (g·cm-3) (kPa·m2·g-1) (%)

0 16 27.3±1.0 3.85±0.05 0.54±0.02 1.35±0.06 63.9±0.6

t
ip
1000 23 45.2±0.8 4.51±0.10 0.66±0.04 3.20±0.08 56.3±0.4

cr
2000 36 57.3±1.1 5.35±0.07 0.71±0.04 4.90±0.12 53.0±0.7

3000 50 68.1±0.7 5.75±0.11 0.75±0.03 7.15±0.04 50.1±0.3

us
E: Young's Modulus

an
M
e d
pt
ce
Ac

Page 28 of 35
Table(s)

Table 3. Effect of CNF from fractionated eucalyptus sawdust addition on the

properties of unbleached unrefined pulp (± standard deviation).

CNF Tensile index E Density Burst index Porosity

ºSR
(%) (N·m·g-1) (GPa) (g·cm-3) (kPa·m2·g-1) (%)

0 16 27.3±1.0 3.85±0.05 0.54±0.02 1.35±0.06 63.9±0.6

t
ip
3 22 37.0±0.7 4.25±0.12 0.57±0.01 2.95±0.11 61.8±0.3

cr
6 26 41.3±0.9 5.95±0.08 0.64±0.01 4.70±0.12 57.1±0.7

9 34 53.3±1.1 5.95±0.05 0.66±0.03 6.10±0.09 55.9±0.5

us
E: Young's Modulus

an
M
e d
pt
ce
Ac

Page 29 of 35
Figure(s)

i
cr
us
an
M
ed
pt
ce
Ac

Page 30 of 35
Figure(s)

i
cr
us
an
M
ed
pt
ce
Ac

Page 31 of 35
Figure(s)

t
ip
cr
us
an
M
d
te
p
ce
Ac

Page 32 of 35
Figure(s)

i
cr
us
an
M
ed
pt
ce
Ac

Page 33 of 35
Figure(s)

i
cr
us
an
M
ed
pt
ce
Ac

Page 34 of 35
Supplementary data

Graphical abstract

t
ip
cr
us
an
M
e d
pt
ce
Ac

Page 35 of 35