Cellulose (2009) 16:481489 DOI 10.

1007/s10570-009-9279-z

Dyeing behaviour of lyocell fabric: effect of NaOH pre-treatment

Parikshit Goswami Richard S. Blackburn Jim Taylor Patrick White

Received: 6 November 2007 / Accepted: 25 January 2009 / Published online: 11 February 2009 Springer Science+Business Media B.V. 2009

Abstract To understand the effect of alkali pretreatment on the dyeing of lyocell fabrics, samples are pre-treated with 0.07.0 mol dm-3 NaOH using a pad-batch process and then dyed with different types of reactive dyes. Exhaustion, xation, and visual colour strength (K/S values) are measured. It is observed that sodium hydroxide pre-treatment significantly improves the colour yield, exhaustion, and xation for all dyes used. Highest K/S values are obtained when the fabrics are pre-treated with 2.0 2.5 mol dm-3 NaOH. Cross-sectional analysis shows that below this optimum concentration the core bres in the yarn are not dyed; at optimum concentration all bres in yarn cross-section are homogeneously dyed. Cross-sectional analysis shows that as the pre-treatment concentration of NaOH increases above 2.5 mol dm-3, the bres change progressively from a circular to angular cross-section, forming a solid unit. The decrease in K/S above the treatment concentration of 2.5 mol dm-3, though the %E and %F remains almost constant, is attributed to the

distribution of dye over a larger surface area of the outer bres in the yarn cross section, forcing the K/S at kmax to decrease. Keywords Regenerated cellulose Cellulose II Sodium hydroxide Swelling Reactive dyes Diffusion Morphology

Introduction Cellulose is the most abundant biopolymer (Klemm et al. 2005) and of particular interest in providing renewable, sustainable, biodegradable biopolymers for industrial applications. Cellulose is a linear 1,4-bglucan polymer; the units are able to form highly ordered structures, as a result of extensive interaction through intra- and intermolecular hydrogen bonding of the three hydroxyl groups in each glucose unit. We have recently provided (Goswami et al. 2009) an extensive review of the treatment of cellulose with sodium hydroxide (NaOH); alkali has a substantial inuence on morphological, molecular and supramolecular properties of cellulose, causing changes in crystallinity, pore structure, accessibility, stiffness, unit cell structure and orientation of brils in cellulosic bres. Treatment with alkali can improve mechanical and chemical properties of cellulose bres such as dimensional stability, brillation tendency, dyeability, reactivity, lustre and fabric smoothness. Factors such as the concentration of NaOH, treatment temperature,

This paper was presented at the 2nd International Cellulose Conference, Tokyo, Japan, 24th October 2007. P. Goswami R. S. Blackburn (&) Green Chemistry Group, Centre for Technical Textiles, University of Leeds, Leeds LS2 9JT, UK e-mail: r.s.blackburn@leeds.ac.uk J. Taylor P. White Lenzing Fibers, Lenzing, Austria

123

482

Cellulose (2009) 16:481489

applied tension, residence time, source of cellulose, physical state of cellulose (bril, bre, yarn or fabric), and degree of polymerisation have an effect on the properties and degree of change upon treatment (Heinze and Wagenknecht 1998; Colom and Carrillo 2002; Jaturapiree et al. 2006; Manian et al. 2008). In general, there is limited research in this area on cellulose II polymers; researchers have concluded that when cellulose I is converted to cellulose II the crystallinity index decreases, therefore, it is interesting to understand the change in crystallinity of cellulose II polymers when treated in alkali, particularly considering the increasing demand for lyocell bres. Lyocell bres may be dened as cellulosic bres that are produced by regenerating cellulose into bre form out of a solution in an organic solvent (Albrecht et al. 1997). Solvent spun lyocell bres consist of crystalline cellulose II and amorphous cellulose and have a higher degree of crystallinity (80%) in comparison with other regenerated cellulosic bres, such as modal (49%) and viscose (41%) (Colom and Carrillo 2002). The high degree of crystallinity in lyocell is a consequence of higher orientation during stretching and formation of bres; lyocell bres have the thinnest and longest crystallites, even the amorphous regions are oriented along the bre axis (Kreze and Malej 2003). Lyocell bres spun from cellulose solution in N-methylmorpholine-N-oxide (NMMO) hydrate have proven commercially successful in textile and nonwoven products due to their excellent mechanical properties in the wet state, when compared with viscose rayon (Loubinoux and Chaunis 1987; Lenz et al. 1993; Mortimer and Peguy 1996; Chae et al. 2002). The manufacturing process is environmentally benign because the non-toxic, biodegradable NMMO solvent used is almost completely recycled (Woodings 1995; Albrecht et al. 1997; Schuster et al. 2004). Additionally, the spinning baths are ltered, cleaned, upgraded and then fed back into the system and the proportion of used NMMO recovered in practice is over 99.5%. The efciency of the system developed is such that the consumption of NMMO can be kept down to a few kilograms per tonne of bre produced (Lennox-Kerr 1994; Albrecht et al. 1997). The life cycle of a lyocell bre has minimal environmental impact and it is argued that the bre is signicantly more sustainable than oilderived synthetic bres (e.g., polyester, nylon, acrylic) and natural bres such as cotton (which

requires signicant areas of land, irrigation, pesticides and fertilizers to grow, which the eucalyptus trees, from which lyocell is made, do not; White et al. 2005). Due to the unique highly crystalline structure of lyocell, and weaker lateral links between the crystallites, the bres undergo localized separation of brous elements at the surface known as brillation, mainly under conditions of wet abrasion (Zhang et al. 2005; Abdullah et al. 2006). Fibrillation is the longitudinal splitting of a single bre into microbres of typically less than 14 lm in diameter (Chavan and Patra 2004). This brillation behaviour restricts the applications of lyocell; in particular, fabric dyed in dark hues, as medium/heavy depths can develop a frosty (greying) appearance caused by very ne brils that are visually transparent; we have demonstrated previously (Goswami et al. 2007) that brillated lyocell shows lower visual colour yield in comparison with non-brillated lyocell, independent of exhaustion and xation. If brillation is not controlled, these microbres become entangled giving a serious problem of pilling. Processing of lyocell is more technically challenging in fabric and garment form compared to other regenerated cellulosic bres due to brillation (Bates et al. 2004), and for overall success in the textile industry, it is important to understand the dyeing behaviour of brillated lyocell thoroughly to overcome this problem. Colom and Carrillo (2002) studied the effect of sodium hydroxide treatment on crystallinity in the cellulose II polymers lyocell, modal and viscose, and followed this with a separate study comparing lyocell, acid-hydrolysed lyocell, and standard crystalline cellulose I (Carrillo et al. 2004). Recently, we have observed (Goswami et al. 2009) that sodium hydroxide treatment causes the density, orientation and crystallinity of lyocell bre to decrease with increasing sodium hydroxide concentration, and that the greatest change in bre properties occurs between 3.0 and 5.0 mol dm-3 NaOH. This was attributed to the onset of formation of sodium(Na)-cellulose II at 3.0 mol dm-3 NaOH; a fully formed Na-cellulose II structure was observed above 6.8 mol dm-3 NaOH. The work concluded that formation of Na-cellulose II causes plasticization of the lyocell bres as both inter- and intra-molecular hydrogen bonds are broken by these higher sodium hydroxide concentrations. In this study, lyocell fabrics were pre-treated with varying concentrations of sodium hydroxide and then

123

Cellulose (2009) 16:481489

483

dyed with nine different types of reactive dyes in order to ascertain the optimum concentration of NaOH that can afford high colour yield.

Experimental Materials De-sized, 100% lyocell, 2 9 1 twill, ring spun warp (1/22 Ne; 40 ends cm-1), open end spun weft (1/12 Ne; 22 picks cm-1), 240 g m-2 was supplied by Lenzing Austria. Samples of Procion Deep Red H-EXL, Procion Red H-E3B (C.I. Reactive Red 120), Procion Yellow H-E6G (C.I. Reactive Yellow 135), Procion Yellow H-EXL (C.I. Reactive Yellow 138:1), Procion Navy H-EXL, and Procion Orange H-ER (C.I. Reactive Orange 84) were kindly supplied by DyStar, Germany. Samples of Cibacron Brilliant Red 4G-E, Cibacron Navy W-B (C.I. Reactive Black 5), and Cibacron Orange 4R (C.I. Reactive Orange 35) were kindly supplied by Ciba, Switzerland. The dyeing auxiliary Sandozin NIN (non-ionic surfactant) was supplied by Clariant, UK. Embedding liquor JB-4 was supplied by Agar Scientic. All other chemicals were supplied by Aldrich. Methods Scouring Lyocell fabric was scoured in a Roaches Rotohose rotary drum dyeing machine for 15 min at 60 C with 1 g dm-3 Sandozin NIN and 2 g dm-3 sodium carbonate using a liquor ratio of 20:1. Alkali pre-treatment Lyocell fabrics were treated with aqueous concentrations of NaOH between 0.07.0 mol dm-3 by a padbatch process. Samples were immersed in an aqueous NaOH solution, passed through an Ernst Benz padding mangle applying a pressure of 10 kg cm-2, and then batched for 30 min by wrapping around a glass rod and enveloping the sample in poly(ethylene) sheet. The samples were subsequently removed from the glass rod, rinsed in hot water for 5 min, and then immersed in 5% aqueous acetic acid at room temperature for 60 min. Samples were then rinsed

in cold water for 5 min and dried. The pH of the samples was measured by a Werner Mathis MorapexA machine, which passes distilled water through the sample at 40 C and measures the pH of the resultant solution. Wet pick-up of the samples is calculated using Eq. 1, where W is the weight of the sample after padding and D is the dry weight of the sample:   W D Wet pick up 100 1 D Dyeing Lyocell fabric samples (10 g) were dyed with reactive dyes at 2% on mass of bre (omf) in a Mathis Air Boy dyeing machine, using a liquor ratio of 20:1, according to the methods shown in Figs. 1 and 2 for Procion and Cibacron dyes, respectively. After dyeing the fabric samples were thoroughly rinsed with cold water, then washed for 30 min at 95 C using a liquor ratio of 20:1, and dried at at ambient conditions. Colour measurement After drying, samples were measured using a Datacolor SF600 Spectraash colour spectrophotometer connected to a personal computer using DCI Colour Tools software. From reectance values (R) at a specied wavelength (k) of the dyeings, the colour strength (K/S) of the sample was calculated using the Kubelka-Munk equation (Eq. 2; McDonald 1980): K =S 1 Rk 2 2 Rk 2

Fig. 1 Dyeing prole for dyeing lyocell with Procion dyes

123

484
170 160 150

Cellulose (2009) 16:481489

47 46 45 44 43 42 41 40 % wet pick-up xc (%) 0 2 4 6
-3

% wet pick-up

140 130 120 110 100 90 80

39 38

NaOH (mol dm )

Fig. 2 Dyeing prole for dyeing lyocell with Cibacron dyes

UV/visible spectrophotometry The exhausted dyebaths, and wash-off liquors were measured using a PerkinElmer Lambda 9 UV/ Visible/NIR spectrophotometer in the visible region of the spectrum (400700 nm), at 2 nm intervals. Concentrations were calculated from calibration graphs at the wavelength of maximum absorption (kmax). The residual dye solutions were diluted using distilled water and measured at kmax and the concentration of residual dye in solution calculated from calibration plots, and dye adsorbed by the bre calculated from the difference before and after exhaustion. No difference in the shape of the absorption spectrum before and after dyeing was noted. Cross-sectional analysis After dyeing, alkali pre-treated samples were embedded in resin using a JB-4 embedding kit and 6 lm cross-sections cut using a Beck Microtome. These sections were analysed and pictures taken using an Olympus BH-2 optical microscope attached to a digital camera system.

Fig. 3 Comparison of % crystallinity (xc; Goswami et al. 2009) and % wet pick-up with increasing NaOH concentration in the pre-treatment bath

in the pre-treatment bath xc decreases, accompanied by a corresponding increase in % wet pick-up. It is logical that as crystallinity of the cellulose II bre (and associated hydrogen bonding) decreases, the sorption of water by the lyocell bre will increase, as a result of a greater potential for hydrogen bonding between water molecules and the bre and increased swelling of the bre. Exhaustion (%E), xation (%F) and K/S values at kmax (colour strength) of NaOH pre-treated lyocell dyed with Procion and Cibacron reactive dyes were calculated, and it is found that, in general, the trends observed were similar for each dye. A representative example is shown in Fig. 4 for C.I. Reactive Red

Results and discussion It is noted that all alkali pre-treated samples show very little variation in pH (6.56.8) after neutralisation. Figure 3 shows a comparison between % crystallinity (xc; Goswami et al. 2009) and % wet pick-up, and it is observed that with increasing concentration of NaOH

Fig. 4 Comparison of K/S values at kmax, % Exhaustion, and % Fixation for lyocell treated with different concentrations of NaOH for C.I. Reactive Red 120 (structure shown)

123

x c (%)

Cellulose (2009) 16:481489

485

120, where it is observed that NaOH pre-treatment improves the colour strength at all concentrations with respect to the untreated sample. The trend observed is that initially as concentration of NaOH in the pre-treatment stage increases, resultant colour strength also increases accompanied by similar increases in %E and %F, to a maximum at around 2.02.5 mol dm-3 NaOH. Cross-sectional analysis was performed on alkali pre-treated lyocell yarns taken from the fabrics that had
Fig. 5 Optical crosssections of lyocell laments in a yarn dyed with 2% omf Cibacron Brilliant Red 4G-E following pretreatment with: a 0.0 mol dm-3 NaOH; b 1.5 mol dm-3 NaOH, c 2.0 mol dm-3 NaOH, d 5.0 mol dm-3 NaOH, and e 7.0 mol dm-3 NaOH. Scale bar is 20 lm

been dyed with Cibacron Brill Red 4G-E (Fig. 5) and C.I. Reactive Black 5 (Fig. 6). It is observed that the bres in the core of the yarn have signicantly less dye when the lyocell had not been pre-treated with alkali (Figs. 5a, 6a) and when the alkali concentration in the pre-treatment bath was low (up to 1.5 mol dm-3; Figs. 5b, 6b), and most of the dye adsorbed is located at the periphery of the yarn. However at a concentration of 2.0 mol dm-3 NaOH (Figs. 5c, 6c), is it seen that all the bres in the yarn cross-section are uniformly dyed;

123

486 Fig. 6 Optical crosssections of lyocell laments in a yarn dyed with 2% omf C.I. Reactive Black 5 following pre-treatment with: a 0.0 mol dm-3 NaOH, b 1.5 mol dm-3 NaOH, c 2.0 mol dm-3 NaOH, d 5.0 mol dm-3 NaOH, and e 7.0 mol dm-3 NaOH. Scale bar is 20 lm

Cellulose (2009) 16:481489

this nding is in agreement with the ndings of Bui et al. (2008), where they reported an increase in porosity and accessibility in lyocell bres after treatment with NaOH solution. The increase in %E, %F, and K/S from concentrations of 0.02.0 is attributed to a decrease in density and crystallinity of lyocell bre with increasing concentration of NaOH in the pre-treatment bath (Goswami et al. 2009); as adsorption and diffusion of dyes only occurs

in the amorphous regions of a bre this decrease in crystallinity affords the corresponding increase in dye sorption. In spite of this phenomenon, at concentrations of NaOH above 2.02.5 mol dm-3, the K/S values decrease with increasing NaOH concentration to a plateau around 5.0 mol dm-3 NaOH. %E and %F, in general, are constant after 2.53.0 mol dm-3 NaOH, hence, the observed decrease in K/S values must be

123

Cellulose (2009) 16:481489

487

due to some other reason. Observing the location of the dyes through the yarn cross-section at NaOH pretreatment concentrations of 5.0 mol dm-3 (Figs. 5d, 6d) and 7.0 mol dm-3 (Figs. 5e, 6e), it is observed again that there is a higher concentration of dye located in the peripheral bres in comparison with the bres in the centre of the yarn, even though the overall %E is higher in comparison with lower concentrations. It was also observed from the cross-sections that with increasing NaOH concentration, the bres in the yarn cross-section changed from a circular shape to a more angular shape; deformation of the bres occurs because, in the presence of NaOH, the bres swell (Goswami et al. 2009). It is proposed that with increasing NaOH concentration the extent of hydrogen bonding in cellulose is reduced and the degree of swelling increases; the internal voids in the twisted yarns become limited, neighbouring bres are squeezed together with increasing pressure, the bres deform to occupy the voids forming a solid unit, and the bres lose there circular cross-section. After the pretreatment process and subsequent rinsing the bres contract again opening up voids once more, but the bres retain their angular shape and do not revert to a circular cross-section. On subsequent dyeing of lyocell fabrics that have been pre-treated at higher NaOH concentrations, in the aqueous dyebath the lyocell reforms the solid unit on swelling and it becomes difcult for the dye molecules to diffuse within the interior of the yarn. Only the surface bres are dyed where the cellulose sorption surface is exposed to the dye solution; the core of the yarn is virtually undyed. However, even though the bres in the core of the yarn remain undyed the exhaustion and xation remain almost the same above 2.53.0 mol dm-3 NaOH. We have observed previously (Goswami et al. 2009) that the greatest change in lyocell bre properties, when treated with NaOH occurs between 3.0 and 5.0 mol dm-3. This is attributed to the onset of the formation of Na-cellulose II at 3.0 mol dm-3 NaOH; a fully formed Na-cellulose II structure is expected above 6.8 mol dm-3 NaOH. Formation of Na-cellulose II causes plasticization of lyocell bres as both inter- and intra-molecular hydrogen bonds are broken by these higher NaOH concentrations. This decrease in the density and crystallinity of the bre enhances the sorption properties of the outer bres of the yarn cross-section. It was demonstrated in our

Fig. 7 Comparison between the change in cross-sectional area and K/S at kmax for samples dyed with Procion Deep Red HEXL over the concentration range 2.06.0 mol dm-3 NaOH

previous work that above a pre-treatment concentration of 5.0 mol dm-3 NaOH there is very little, if any, further change in density and crystallinity, hence explaining the observation herein that %E and %F remain constant above 3.0 mol dm-3 NaOH. Figure 7 shows the relationship between the change in cross-sectional area (Goswami et al. 2009), and the change in K/S at kmax (example is Procion Deep Red H-EXL) including the critical range of 3.05.0 mol dm-3 NaOH, where cellulose II is converted to Na-cellulose II. Sigmoidal tting of the experimental results in Fig. 7 enables correlation between variations of these parameters with sodium hydroxide concentration. From the sigmoidal tting, Eq. 3 is derived, where COH(s) is the sodium hydroxide concentration in aqueous solution and Y refers to the physical property (i.e., cross-sectional area or K/S at kmax), all the other parameters are constants and their values given in Table 1, which also provides the R2 value of each sigmoidal t: Y A0 A1 A0   C s B 0 1 exp OHB 1 3

Both cross-sectional area and K/S show very high correlation with the sigmoidal t over the concentration range, where it is observed that as NaOH concentration increases, cross-sectional area increases and K/S decreases;. It is proposed that in the range 2.0 6.0 mol dm-3 NaOH, as the cross-sectional area increases, the adsorbed dyes are distributed over a greater surface area of the bres, which causes a visual

123

488

Cellulose (2009) 16:481489

Table 1 Constants in above equation and correlation (R2) for sigmoidal tting of experimental data based on various parameters Y Cross sectional area K/S at kmax A0 112.78421 19.13863 A1 146.49800 15.93243 B0 4.50622 3.03225 B1 0.52329 0.40927 R2 0.99999 0.99956

effect of the dyeing appearing lighter, explaining the decrease in K/S within this range. Conclusions It was observed that NaOH pre-treatment signicantly improves the colour yield, exhaustion, and xation for all dyes used. Highest K/S values are obtained when the fabrics are pre-treated with 2.02.5 mol dm-3 NaOH. Cross-sectional analysis shows that, below this optimum concentration, the core bres in the yarn are not dyed; at optimum concentration, all bres in yarn cross-section are homogeneously dyed. Cross-sectional analysis shows that as the pre-treatment concentration of NaOH increases the bres change progressively from a circular to angular cross-section, forming a solid unit. The decrease in K/S above the treatment concentration of 2.53.0 mol dm-3, though the %E and %F remain almost constant, is attributed to the distribution of adsorbed dye over a larger surface area of the outer bres in the yarn cross section, causing the decrease in K/S.
Acknowledgments The authors would like to thank Lenzing AG and The UK Government (Overseas Research Scholarship Awards Scheme) for the provision of a PhD scholarship to Mr. Goswami.

References
Abdullah I, Blackburn RS, Russell SJ, Taylor J (2006) Abrasion phenomena in twill tencel fabric. J Appl Polym Sci 102:13911398. doi:10.1002/app.24195 Albrecht W, Reintjes M, Wulfhorst B (1997) Lyocell bers. Chem Fibers Int 47:298304 Bates I, Mauchru E, Phillips DAS, Renfrew AHM, Su Y, Xu J (2004) Cross-linking agents for the protection of lyocell against brillation: synthesis, application and technical assessment of 2,4-diacrylamidobenzenesulphonic acid. Color Technol 120:293300. doi:10.1111/j.1478-4408. 2004.tb00233.x Bui HM, Lenninger M, Manian AP, Abu-Rous M, Schimper CB, Schuster KC, Bechtold T (2008) Treatment in swelling solutions modifying cellulose ber reactivity part 2 accessibility reactivity. Macromol Symp 262:5064

ol JJ, Saurina J (2004) Structural Carrillo F, Colom X, Sun FTIR analysis and thermal characterisation of lyocell and viscose-type bres. Eur Polym J 40:22292234. doi: 10.1016/j.eurpolymj.2004.05.003 Chae DW, Chae HG, Kim BC, Oh YS, Jo SM, Lee WS (2002) Physical properties of lyocell bers spun from isotropic cellulose dope in NMMO monohydrate. Text Res J 72:335340. doi:10.1177/004051750207200410 Chavan RB, Patra AK (2004) Development and processing of lyocell. Indian J Fibre Text Res 29:483492 Colom X, Carrillo F (2002) Crystallinity changes in lyocell and viscose-type bres by caustic treatment. Eur Polym J 38:22252230. doi:10.1016/S0014-3057(02)00132-5 Goswami P, Blackburn RS, Taylor J, Westland S, White P (2007) Dyeing behav lyocell fabric effect brillation. Color Technol 123:387393 Goswami P, Blackburn RS, El-Dessouky HM, Taylor J, White P (2009) Effects of sodium hydroxide pre-treatment on the optical and structural properties of lyocell. Eur Polym J 45:455465. doi:10.1016/j.eurpolymj.2008.10.030 Heinze U, Wagenknecht W (1998) Comprehensive cellulose chemistry: functionalisation of cellulose. Wiley-VCH, Weinheim Jaturapiree A, Manian AP, Bechtold T (2006) Sorption studies on regenerated cellulosic bers in salt-alkali mixtures. Cellulose 13:647654. doi:10.1007/s10570-006-9069-9 Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:237. doi:10.1002/anie. 200460587 Kreze T, Malej S (2003) Structural characteristics of new and conventional regenerated cellulosic bers. Text Res J 73:675684. doi:10.1177/004051750307300804 Lennox-Kerr P (1994) Natural bres and composites. Tech Text Int 3(July/August):1819 Lenz J, Schurz J, Wrentscur E (1993) Properties and structure of solvent-spun and viscose-type bres in the swollen state. Colloid Polym Sci 271:460468. doi:10.1007/ BF00657390 Loubinoux D, Chaunis S (1987) An experimental approach to spinning new cellulose bers with N-methylmorpholineoxide as a solvent. Text Res J 57:6165. doi:10.1177/ 004051758705700201 Manian AP, Abu-Rous M, Lenninger M, Roeder T, Schuster KC, Bechtold T (2008) The inuence of alkali pretreatments in lyocell resin nishingber structure. Carbohydr Polym 71:664671. doi:10.1016/j.carbpol. 2007.07.020 McDonald R (1980) Industrial pass-fail color matching. 3. Development of a pass-fail formula for use with instrumental measurement of color difference. J Soc Dyers Col 96:486496

123

Cellulose (2009) 16:481489 Mortimer SA, Peguy AA (1996) The formation of structure in the spinning and coagulation of lyocell bres. Cellulose Chem Technol 30:117132 Schuster KC, Rohrer C, Eichinger D, Schmidtbauer J, Aldred P, Firgo H (2004) In: Wallenberger FT (ed) Natural bres, plastics and composites. Kluwer Academic Publishers, London White P, Hayhurst M, Taylor J, Slater A (2005) In: Blackburn RS (ed) Biodegradable and sustainable bres. Woodhead Publishing Limited, Cambridge

489 Woodings CR (1995) The development of advanced cellulosic bres. Int J Biol Macromol 17:305309. doi:10.1016/ 0141-8130(96)81836-8 Zhang WS, Okubayashi S, Bechtold T (2005) Fibrillation tendency of cellulosic bers. Part 1: effects of swelling. Cellulose 12:267273. doi:10.1007/s10570-004-2786-z

123