Cellulose (2008) 15:3545 DOI 10.

1007/s10570-007-9143-y

Chemical surface modications of microbrillated cellulose

Per Stenstad Martin Andresen Bjrn Steinar Tanem Per Stenius

Received: 16 March 2007 / Accepted: 8 July 2007 / Published online: 25 July 2007 Springer Science+Business Media B.V. 2007

Abstract Microbrillated cellulose (MFC) was prepared by disintegration of bleached softwood sulphite pulp through mechanical homogenization. The surface of the MFC was modied using different chemical treatments, using reactions both in aqueousand organic solvents. The modied MFC was characterized with fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Epoxy functionality was introduced onto the MFC surface by oxidation with cerium (IV) followed by grafting of glycidyl methacrylate. The length of the polymer chains could be varied by regulating the amount of glycidyl methacrylate added. Positive charge was introduced to the MFC surface through grafting of hexamethylene diisocyanate, followed by reaction with the amines. Succinic and maleic acid groups could be introduced directly onto the MFC

surface as a monolayer by a reaction between the corresponding anhydrides and the surface hydroxyl groups of the MFC. Keywords Microbrillated cellulose MFC Nanobrillar cellulose Chemical surface modication Cerium grafting Glycidyl methacrylate Diisocyanate Succinic anhydride Maleic anhydride Abbreviations CDI Carbonyl diimidazole DABCO 1,4-Diazabicyclo[2.2.2]octane DEAPA 3-(Diethylamino) propylamine FTIR Fourier transform infrared spectroscopy GMA Glycidyl methacrylate HMDI Hexamethylene diisocyanate MFC Microbrillated cellulose SEC Size exclusion chromatography THF Tetrahydrofuran XPS X-ray photoelectron spectroscopy TEM Transmission electron microscopy

P. Stenstad (&) B. S. Tanem SINTEF Materials and Chemistry, Trondheim 7465, Norway e-mail: per.m.stenstad@sintef.no M. Andresen P. Stenius Ugelstad Laboratory, Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim 7491, Norway P. Stenius Helsinki University of Technology, Otakaari 1, Espoo 02150, Finland

Introduction Microbrillar cellulose, MFC, is a basic structural component of wood bers. The potential utilization of the unique properties of MFC as a renewable, abundant and biodegradable natural product in

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advanced innovative applications has attracted increasing interest. The preparation of MFC derived from wood was introduced by Turbak et al. more than two decades ago (Turbak et al. 1983; Herrick et al. 1983). Through a homogenization process, wood pulp is disintegrated, giving a material where the bres are moderately degraded and opened into their sub-structural brils and microbrils. The microbrils are 150 nm thick and have a length of several lm, and can thus be regarded as nanobres. Their strength, exibility and aspect ratio suggest a host of tentative possibilities to utilize MFC in large-scale applications. For example, its exceptionally large specic surface area implies potential increased interactivity with secondary components/ materials. This could create innovative breakthroughs in use of these materials in areas such as e.g. nanocomposites, packagings, coatings and dispersion technology. MFC has also been proposed as a rheology modier in foods, paints, cosmetics and pharmaceutical products (Turbak et al. 1983; Herrick et al. 1983). Furthermore, much work has been done preparing nanocomposites reinforced with MFC (Nakagaito and Yano 2004, 2005) or with brillated cellulosic materials from other sources than wood, including parenchymal microbrils (Azizi Samir et al. 2004; Malainine et al. 2005; Bruce et al. 2005) and bacterial cellulose (Nakagaito et al. 2005). The surface of cellulose microbrils carries a large number of hydroxyl groups, which makes the microbrils suitable for introduction of new functionality in heterogeneous reactions. However, reports on chemical modication of MFC surfaces are very limited. The vast majority of cellulose derivatives are prepared by chemical modication of dissolved cellulose, i.e. homogenous derivatization (Heinze and Liebert 2001). Typical modications start by esterication or etherication of the hydroxyl groups. Many commercial cellulose ethers and cellulose esters are produced in this way. Several studies of chemical surface modication of cellulose bres have been published. For reviews m and of such work, see e.g. Isogai (2001), Lindstro gberg (2002). In studies of the effects of bre Wa surface chemistry on the mechanical properties of cellulose-bre-reinforced polymer composites, Cai et al. (2003) and Wu et al. (2000) used cellulose bres modied by silanisation. Joseph et al. (1996)

modied cellulose bres with isocyanate compounds in order to prepare a more hydrophobic bre surface. Toledano-Thompson et al. (2005) grafted glycidyl methacrylate on henequen cellulose microbres in order to introduce vinyl groups. In order to improve their hemocompatibility, cellulose membranes have been modied by grafting of betaines (Yuan et al. 2003, Zhang et al. 2003). In recent years a few reports describing surface modication of microbrils have also been published. ` et al. Methods include surface acetylation (Cavaille et al. 2002, 2004), car1997), silanisation (Gousse boxymethylation (Cash et al. 1999) and reaction with isocyanate (Ladouce et al. 2000). In this paper, we report three methods for modication of MFC by heterogeneous reactions in both water and organic solvents, which may be employed in the preparation of novel, multifunctional cellulose nanobre based material concepts. While the reactions as such are well known, their use to introduce polymer brushes, vinyl groups and charge onto MFC surfaces has, to our knowledge, not previously been reported. Particular attention is paid to using reactions and reaction conditions that would conne the functionalization mainly to the surface of the MFC. This is important because otherwise inordinately large amounts of reactants will be consumed by bulk functionalization, which will not contribute to interactions of MFC with a secondary media. Furthermore, too harsh reaction conditions may lead to partial solubilization of the microbrils, as the hydrogen bonds between the cellulose chains in the et al. 2002, 2004; surface are disrupted (Gousse Andresen et al. 2006). Also, penetration into amorphous parts of the microbrils may lead to undesirable degradation of the strength properties of the MFC due to cutting of cellulose chains.

Experimental Chemicals Ammonium cerium (IV) nitrate, hexamethylene diisocyanate, diisopropylamine, maleic anhydride, HNO3 and all solvents were purchased from Merck. DABCO, glycidyl methacrylate, bis-(3-aminopropyl) amine, 3-(diethylamino) propylamine and succinic anhydride were purchased from Fluka.

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Microbrillated cellulose (MFC) Microbrillated cellulose was obtained by disintegration of fully bleached spruce sulphite cellulose (Borregaard VHV-S). To avoid plugging of the homogenizing equipment, the bres were cut to reduce the bre length, which is also believed to increase the rate of homogenization by exposing increased bre cross-sectional area to brillation (Herrick et al. 1983). The pulp was dispersed in water and formed into thick sheets. The wet pulp sheets were then cut by repeated shredding in an ordinary ofce shredder, which resulted in an average bre length of approximately 1 mm. The resulting pulp was diluted to 2% consistency and subjected to 20 passes through a Gaulin M12 homogenizer (from APV), with a pressure drop of 600 bars at each pass. Cerium induced graftingintroduction of glycidyl methacrylate The cerium induced grafting reactions were performed in dilute MFC suspensions, typically 0.1% (w/w) in 0.1 M HNO3. Nitrogen was bubbled through the samples for 15 min prior to addition of ammonium cerium (IV) nitrate to a total end concentration of 2 mM. Then the temperature was increased to 35C while nitrogen was bubbled through the samples under stirring for another 15 min. Glycidyl methacrylate (GMA) was gradually added over a period of 30 min, and the reaction was continued for another 30 min. The amount of glycidyl methacrylate was varied between 2 and 40 lmol/mg MFC. After the polymerization reaction the samples were washed twice with water, then three times with tetrahydrofuran (THF) and nally three times with water. Coating with hexamethylene diisocyanate functionalization with amines The water was removed from the aqueous suspension of MFC by ve washing cycles with acetone. The MFC dispersed in acetone was washed twice with dried THF, after which the brils were redispersed in dry THF to a 0.4% (w/w) suspension. Nitrogen was bubbled through this mixture for 15 min, and the temperature was raised to 50C. Then hexamethylene diisocyanate was added (100 lmol/mg MFC) as well as 0.16% (w/w) 1,4diazabicyclo[2.2.2]octane (DABCO) as a catalyst. The

reaction was performed under stirring for 2 h at 50C. After the reaction the samples were washed twice with dry THF. The samples were ushed with nitrogen during the addition of new solvent to avoid exposure to moisture in the air and prevent hydrolysis of free isocyanate groups. Isocyanate coated MFC was immediately reacted with two different diamines, bis-(3-aminopropyl) amine and 3-(diethylamino) propylamine. The diamines were dissolved in dry THF. The amount was 200 lmol/mg MFC in both cases. Nitrogen was bubbled through the mixtures for 15 min, and the reaction mixtures were stirred for 2 h at 50C. After the reaction the samples were washed ve times with methanol. Grafting of anhydrides Solvent exchange was performed as described for the diisocyanate reaction above, and the MFC was dispersed in dry THF to a 0.4% (w/w) suspension. Diisopropylamine (50 lmol/mg MFC) was added to MFC suspensions as a catalyst, and nitrogen was bubbled through the samples for 10 min. Succinic or maleic anhydride were dissolved in dry THF to a concentration of 0.8 M, and the solutions were added to the MFC suspensions to an end concentration of 200 lmol/mg MFC. The reaction mixture was allowed to stand for 20 h with continuous stirring at 20C. After the reaction the samples were washed ve times with water. FTIR spectroscopy The infrared spectra were obtained on a Perkin Elmer Spectrum One spectrometer. The samples were dried and analyzed using an ATR cell. X-ray photoelectron spectroscopy The XPS analysis was performed on sheets prepared from the modied MFC at Laboratory of Forest Products Chemistry, Helsinki University of Technology in Espoo, Finland. A Kratos AXIS 165 electron spectrometer was used. Survey scans were recorded using monochromated Al Ka irradiation, 0.1 eV step and 80 eV analyzer pass energy. High-resolution spectra were recorded using monochromated Al Ka irradiation, 0.1 eV step and 20 eV analyzer pass

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energy. Three spots on each sample were analyzed. No degradation of the samples under X-ray irradiation was detected. All spectra were corrected for the presence of a low amount of surface contaminations in the spectrometer. For details, see Andresen et al (2006), Johansson et al (1999). Transmission electron microscopy A single droplet of MFC suspension in water was allowed to oat onto, and eventually through, a copper grid covered with a holey carbon lm. The copper grids with the dried microbrils were then allowed to oat on a 2% (w/w) aqueous suspension of uranyl acetate for 3 min. The grids were rinsed, dried and mounted in a Philips CM30 TEM operated at 150 kV. Zeta potential Zeta potentials of MFC samples were obtained on a Malvern Zetasizer Nano ZS instrument. The measurements were performed in a 0.01% (w/w) suspension of MFC in 0.01 M phosphate buffer at pH 7.0.

Results and discussion Cerium induced grafting The cerium (IV) ion is a powerful oxidation agent for alcohols containing 1,2-glycol groups. The mechanism of ceric ion reaction involves the formation of a
Fig. 1 Oxidation of 1,2glycol groups followed by grafting of glycidyl methacrylate
CH2OH O O OH OH O + Ce
4+

chelate complex that decomposes to generate free radicals on the cellulose backbone. In the presence of glycidyl methacrylate (GMA) monomers, these free radicals will generate graft polymerization on the surface of the bres, as shown in Fig. 1 (mechanism proposed by Mishra et al. (2003)). For each GMA monomer added to the polymer chain a new ester group is introduced. The peak at 1722 cm1 in the FTIR spectrum in Fig. 2 shows that a large amount of ester groups were introduced, indicating that polymer chains of GMA were grafted on MFC. Furthermore, the peaks at 845 cm1 and 905 cm1 show that epoxy groups were introduced on the microbrils. The high-resolution C 1s peak in the XPS spectrum of the brils gives information on carbon chemistry. The carbon 1s binding energy depends on the number of bonds between the carbon and oxygen. Generally, the carbon signal can be resolved into four different peaks: C1, originating from carbons bonded only to other carbon atoms or to hydrogen and the C2, C3 and C4 peaks that originate from carbon atoms with one, two (or one double) and three oxygen bonds, respectively (see Fig. 3). Pure cellulose does not contain any carbon that is not bound to oxygen and only negligible amounts of carboxylic groups, and will therefore mainly show C2 and C3 peaks. When GMA is grafted onto the MFC surface, three carbons corresponding to C1, three carbons corresponding to C2, and one carbon corresponding to C4 are introduced for each monomer of GMA introduced. Therefore the intensity of the C1
CH2OH O O OH OH Ce
4+

CH2OH O O O O

.
OH

OH

CH2 OH O O O

CH2 OH O CH3 O O C O O CH 2CH O CH2 O O CH3

2

OH

CH2

[CH

C C O

]n

CH2 CH
O

CH2

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Cellulose (2008) 15:3545 Fig. 2 FTIR spectrum of GMA grafted on MFC compared with that of untreated MFC (dashed line). The strong peak at 1722 cm1 shows that a high amount of carboxyl groups are introduced, which in turn indicates that relatively long chains of poly-GMA are grafted on the MFC surface

39

and C4 peaks will increase while the relative intensity of the C2 and C3 peaks will decrease as the polymer chain grows. That this was indeed the case is illustrated in Fig. 3, which shows the high-resolution spectra of the C 1s peak in native MFC and in MFC grafted with 1.9 and 38 lmol GMA/mg MFC respectively. Figure 4 shows the relative peak areas as a function of the added amounts of GMA. The decrease in the C2 and C3 peaks and the increase in the C1 and C4 peaks conrm that the length of the polymer chains increased when the amount of added GMA was increased. Thus, it was possible to regulate the length of the polymer chains on the MFC surface by varying the amount of GMA. Figure 5 shows transmission electron micrographs of MFC coated with GMA (20 lmol GMA/mg MFC) and of native MFC. While the surface of the unmodied microbrils appears fairly smooth, the modied brils display a more barbed nature, and at large magnication one can clearly see that a polymer layer of substantial thickness is covering the bril surface (Fig. 5, lower right). The wider areas along the GMA coated brils might indicate that amorphous and crystalline regions have undergone different degrees of substitution during the reaction. It is well known that along the transverse direction of the microbrils there are localized distortions of paracrystalline character, with increased susceptibility for chemical treatments (Larsson et al. 1997). One would therefore expect that these amorphous domains are more accessible for cerium induced oxidation and subsequent GMA polymerization. Due to the formation of radicals in the reaction, it is conceivable that the treatment with ammonium cerium nitrate could lead to signicant degradation of the cellulose chains. This was tested by size exclusion

chromatographic analysis of the molecular weight distribution of the cellulose in the MFC after cerium treatment. The analysis was performed at the Akzo Nobel laboratories in Arnhem, The Netherlands. The analysis showed that the distribution before and after treatment with cerium was very similar. The treatment resulted in only a slight reduction in the mean molecular weight detected by SEC. Thus, the effects of the cerium treatment on the strength properties or solubility of the MFC are expected to be negligible. By this method, cellulose nanobres with a surface layer of medium hydrophobicity can be prepared. Furthermore, reactive epoxy groups are introduced, which may serve as starting point for further functionalization with ligands unable to react with the surface hydroxyls in native MFC. The reaction is conducted in aqueous media, and thus the use of potentially hazardous organic solvents and tedious solvent exchange procedures are avoided. The material properties of the MFC is expected to be markedly altered after the introduction of GMA brushes/layers, and work is currently in progress to characterize these properties. An obvious application for such derivatized MFC would be as reinforcement in nanocomposites, where the GMA surface layer is believed to enhance the interfacial interaction between the cellulose microbrils and the hydrophobic polymeric matrix. Another potential use would be as a partially hydrophobic membrane for sub-micrometer particle separation. Diisocyanate functionalization The incorporation of a hydrophobic layer onto the microbril surfaces was also achieved through grafting of diisocyanates. Isocyanate groups react readily

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b Fig. 3 High resolution XPS spectra of the C 1s peak of native

MFC (A) and of MFC grafted with 1.9 lmol GMA/mg MFC (B) and 38 lmol GMA/mg MFC (C)

with hydroxyl groups to form urethane bonds under water-free conditions. When excess amounts of isocyanate are added, the formed urethane groups will react with free isocyanate groups in a second step of the reaction to form allophanate groups (Fig. 6). As indicated in Fig. 6, a new amino group would be introduced for each diisocyanate monomer added in the polymerization reaction, and therefore a crosslinked polymer layer should be formed on the MFC surface by the reaction with a diisocyanate (Sekkar et al. 2003). The FTIR spectrum of diisocyanate coated MFC is given in Fig. 7 and the peak at 2265 cm1 conrms that the polymer layer contained a large amount of isocyanate groups. The introduction of HMDI is further conrmed by the two peaks at 2857 cm1 and 2933 cm1 which are assigned to asymmetric and symmetric CH2 stretch, respectively. The bands at 1615 cm1 and 1576 cm1, assigned to the amide I and amide II vibration, respectively, can be interpreted as the presence of ureic carbonyl groups formed in the crosslinking reaction. As isocyanates react rapidly with water, the coating reaction has to be performed in dry solvents, and any subsequent functionalization would have to be performed immediately after grafting of the isocyanate. The very reactive isocyanate groups were used to introduce amines, such as bis-(3-aminopropyl) amine and 3-(diethylamino) propylamine. Amines react readily with isocyanate to form urea bonds. The abovementioned amines were added to
80 70
Atomic concentration
C1 C2 C3 C4

60 50 40 30 20 10 0 0 5 10 15 20 25 30 35

40

GMA added [mole/mg MFC]

Fig. 4 Relative peak areas of the XPS C 1s peaks of GMA grafted to MFC as a function of the amount of GMA added

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Cellulose (2008) 15:3545 Fig. 5 Transmission electron micrograph of MFC coated with GMA (20 lmol GMA/mg MFC) (right) compared to the native MFC (left)

41

Fig. 6 The reaction between hexamethylene diisocyanate and the MFC surface hydroxyl groups. Isocyanate reacts with a hydroxyl group and a urethane linkage is formed. This group will react with a new isocyanate molecule in a second step, forming an allophanate group

O H
OH + OCN NCO

C N

NCO

NCO
O O H NCO
+

O O C N NCO

C N

C
OCN

O H

OCN

the isocyanate functionalized MFC, in order to introduce positive charge to the surface. The zeta potentials of MFC grafted with bis-(3-aminopropyl)

amine and 3-(diethylamino) propylamine were measured to 13.2 and 14.0 mV, respectively, compared to 9.9 mV of the untreated MFC ( Fig. 8).

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Fig. 7 FTIR spectrum of MFC coated with hexamethylene diisocyanate compared with that of MFC (dashed lines). The peak at 2265 cm1 indicates that the sample contains isocyanate groups, and the peaks at 2857 cm1 and

2933 cm1 show the presence of CH2 groups. Further the peaks at 1615 cm1 and 1576 cm1 can be related to the presence of ureic carbonyl groups, which indicate that the MFC is coated with a crosslinked polymer

Although the use of organic solvents in general, with accompanying solvent exchange, is undesired, it is in this case necessary in order to completely dissolve the highly non-polar diisocyanates and to avoid their hydrolysis. The result is, however, a polymer layer that is far more hydrophobic than what is achieved using GMA as a grafting agent. This, combined with solvent exchange that leaves the amorphous areas on the brils more accessible to derivatization, might lead to partial solubilization of brils into the reaction medium and loss of the initial et al. 2002, Gousse microbrillar structure (Gousse et al. 2004; Andresen et al. 2006). However, as the diisocyanate forms a cross-linked polymer layer on the MFC surface, the cellulose
20 10

chains in the microbril surface are linked together, and this is believed to prevent dissolution of the cellulose polymers in the MFC surface. Like the GMA grafted MFC, cellulose nanobres coated with a highly hydrophobic isocyanate layer have potential use in polymer nanocomposite applications. Furthermore, positively charged amine functionalized MFC could prove to be antimicrobially active in biomedical applications (Thomas et al. 2005). Grafting of anhydrides Succinic and maleic anhydrides (Fig. 9) were coupled to the MFC through reaction with the surface hydroxyls under water-free conditions. When succinic anhydride is reacted with MFC, one expects a layer of acid groups to be introduced on the bril surface. That this was, indeed, the case is demonstrated in the FTIR spectrum in Fig. 10 where the peak at 1724 cm1 veries the presence of carboxyl groups after reaction with succinic anhydride. When maleic anhydride is reacted with MFC hydroxyl groups, vinyl groups will be introduced in

Zeta potential [mV]

0 Ref -10 -20 -30 -40 -50 Succ Maleic Bisamine DEAPA

Fig. 8 Zeta potentials at pH 7.0 of unmodied MFC [Ref], MFC coated with succinic acid [Succ] and maleic acid [Maleic]. Further, the positive zeta potential values were obtained for MFC coated with diisocyanate followed by reactions with bis-(3-aminopropyl) amine [Bisamine] and with 3-(diethylamino) propylamine [DEAPA]

Fig. 9 Structure of maleic and succinic anhydride

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Cellulose (2008) 15:3545 Fig. 10 FTIR spectrum of MFC coated with succinic acid compared with that of MFC (dashed line). The peak at 1724 cm1 shows that carboxyl groups are introduced on MFC

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addition to the acid groups (Fig. 9). That this did occur is shown in the FTIR spectrum in Fig. 11 where the peak at 1722 cm1 conrms the introduction of acid, and the peak at 1636 cm1 indicates that the sample also contained vinyl groups. These vinyl groups could be used as a starting point for grafting reactions for monomers that are insoluble in water, as an alternative to the cerium induced GMA grafting method described above. The samples coated with succinic acid and maleic acid were investigated by XPS. In Fig. 12 the carbon 1s high-resolution spectra of the two samples are compared with that of the unmodied MFC. As can be seen from the structures in Fig. 9, two carbon atoms with no neighboring oxygen will be added to the MFC surface for each acid molecule introduced. This is veried by the XPS spectra, in which the relative intensity of the C1 peaks increased in both cases compared to the unmodied MFC (Fig. 3A). Furthermore, the relative intensity of the C4 peak increased as a result of the introduction of carboxylic groups. The area under the C1 peak corresponds to the amount of the two carbon atoms introduced, while the area under the C3 peak corresponds to the amount of the one carbon/glucose unit that is bound to two oxygen atoms. Therefore the expression (C1/C3)/2 will give a relative estimate of the degree of substitution of the two acids. The values were 0.8 and 0.3 for the succinic and maleic acid respectively, which indicates that the reactivity of succinic anhydride was much higher than that of maleic anhydride. This result was also in agreement with the results from the zeta potential measurements given in Fig. 8, which shows that the zeta potential of MFC coated with succinic acid was 40.9 mV while that of maleic acid was 32.3 mV.

The negatively charged cellulose microbrils resulting from surface modication with anhydrides may have application in nanoscale electronic and optoelectronic devices (Li and Xia 2004). It has also been shown that charged nanobre mats might be good matrices for holding polymer electrolytes and could nd use in the fabrication of high-performance lithium batteries (Choi et al. 2003). Conclusions Some methods of surface modication of MFC were successfully applied in this study. By utilizing the reactions with the free hydroxyl groups in the glucose units of cellulose, MFC surfaces could be activated and functionalized both in aqueous and organic solvent. We have shown that by such modication reactions it is possible to prepare cellulose nanobres with surfaces carrying substantial amounts of epoxy groups, carbon-carbon double bonds, cationic groups (amines) and anionic groups (carboxyls). Also, we have demonstrated the possibility for rendering the MFC hydrophobic by grafting of polymer brushes and layers. The results indicate that the treatments can be designed so that the strength properties or solubility of the MFC are not signicantly changed. However, further studies are required to quantitatively assess the extent of these effects. The surface functionalized cellulose nanobres described herein could be utilized in advanced material applications, including nanocomposites, separation membranes and nanoscale electronic devices, and should have substantial potential as an environmentally benign alternative to synthetic nanobres based on regenerated polymers (Li and Xia 2004).

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44 Fig. 11 FTIR spectrum of MFC coated with maleic acid compared with that of MFC (dashed line). The peak at 1722 cm1 shows that carboxyl groups are introduced onto the MFC, and the peak at 1636 cm1 shows that the sample contains vinyl groups

Cellulose (2008) 15:3545

Fabriker are also gratefully acknowledged for nancial support. Leena-Sisko Johansson at the Laboratory of Forest Products Chemistry, Helsinki University of Technology in Otaniemi, Espoo, Finland is acknowledged for the XPS analysis. Roberta Hofman, Akzo Nobel Functional Chemicals, is thanked for help with the SEC analysis. The Norwegian Paper and Fibre Research Institute is thanked for providing the MFC.

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