Cellulose (2009) 16:7585 DOI 10.

1007/s10570-008-9244-2

Strength and barrier properties of MFC lms

Kristin Syverud Per Stenius

Received: 11 March 2008 / Accepted: 14 July 2008 / Published online: 19 August 2008 Springer Science+Business Media B.V. 2008

Abstract The preparation of microbrillar cellulose (MFC) lms by ltration on a polyamide lter cloth, in a dynamic sheet former and as a surface layer on base paper is described. Experimental evidence of the high tensile strength, density and elongation of lms formed by MFC is given. Typically, a MFC lm with basis weight 35 g/m2 had tensile index 146 18 Nm/g and elongation 8.6 1.6%. The E modulus (17.5 1.0 GPa) of a lm composed of randomly oriented brils was comparable to values for cellulose bres with a bril angle of 50. The strength of the lms formed in the dynamic sheet former was comparable to the strength of the MFC lms prepared by ltration. The use of MFC as surface layer (08% of total basis weight) on base paper increased the strength of the paper sheets signicantly and reduced their air permeability dramatically. FEG-SEM images indicated that the MFC layer reduced sheet porosity, i.e. the dense structure formed by the brils resulted in superior barrier properties. Oxygen transmission rates (OTR) as low as 17 ml m-2 day-1 were obtained for lms prepared from pure MFC. This result fulls the requirements for oxygen transmission rate in modied atmosphere packaging.

Keywords MFC Strength Barrier MFC lms Microbrillar cellulose Nano cellulose Paper

Introduction The production of microbrillar cellulose (MFC hereafter) from wood bres was demonstrated by Turbak et al. (1983) in the early 1980s. The smaller dimensions and the large surface area of MFC compared to bres open up for new, perhaps unforeseen possibilities to utilise cellulose-based materials. However, so far protable production of MFC has been restricted by high energy consumption, difculties with up-scaling and runnability problems. During the last years research within this area has increased rapidly and breakthroughs in the production methods are expected (see e.g. Paakko et al. 2007; Abe et al. 2007). It has become relatively easy to produce MFC in laboratory scale, which offers the possibility to perform more extensive research with MFC. Several recent publications demonstrate how MFC can be utilized for various purposes, e.g. in nanocomposites (Nakagaito and Yano 2005; Bruce et al. 2005; Malainine et al. 2005; Lopez-Rubio et al. 2007), as dispersion stabilizers (Oza and Frank 1986; Ougiya et al. 1997; Khopade and Jain 1990; Andresen and Stenius 2007), and as antimicrobial lms (Andresen et al. 2007). However, little has been reported about

K. Syverud (&) Paper and Fibre Research Institute (PFI), Hgskoleringen 6b, NO-7491 Trondheim, Norway e-mail: kristin.syverud@p.no P. Stenius Ugelstad Laboratory, Department of Chemical Engineering, NTNU, Hgskoleringen 6b, NO-7491 Trondheim, Norway

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the use of MFC in paper applications or the properties of pure MFC lms. The decomposition of wood bres into micro- or nanobrillar cellulose gives a material which retains many of the advantageous properties of cellulose bres, such as the ability to form hydrogen bonds, resulting in a strong network. Taniguchi (1998) reports that the tensile strength of a MFC lm from wood pulp is approximately 2.5 times higher than the tensile strength of a printing paper. The type of printing paper or the basis weight of lms and paper are not specied. Production of MFC lms is also described by Dufresne et al. (1998). They use MFC produced from sugar beet pulps and study the inuence of pectins on mechanical properties. Henriksson and Berglund (2007) report an E modulus of 14 GPa for pure MFC lms and E = 16.6 GPa for composite lms of MFC and melamine formaldehyde (MF) containing 9% MF. Petrochemically based polymers predominate in packaging of foods due to their ease of processing, excellent water barrier properties and low cost. However, there is an increasing interest in replacing synthetic polymers with more sustainable materials. The barrier properties of plastics are low in comparison to traditional packaging materials, such as glass and hermetics. Hence, polymer lms with low permeability to low molecular gases, such as O2 and CO2, have been developed. Such polymers are used in connection with modied atmosphere packaging (MAP), where a controlled atmosphere within the packaging is desired (Ackermann et al. 1997). Large efforts have been spent to improve the barrier properties of commonly used plastics such as polyethylene (PE). The crystallinity of the polymers is of large importance for the barrier properties of the polymers (Lagaron et al. 2004). The MFC brils have dimensions in the nanoscale, ranging upwards from less than 10 nm in diameter. It is well known that it is difcult for other molecules to penetrate the crystalline parts of cellulose brils. These properties, in combination with the ability of the dried brils to form a dense network held together by strong inter-brillar bonds, suggest that due to the barrier and strength properties of the lms, MFC may be an interesting alternative to e.g. plastics In the present paper focus is set on the strength and barrier properties of MFC lms prepared from

microbrils from wood cellulose bres. The use of pure MFC and MFC as a layer on base paper in order to increase barrier properties are demonstrated.

Experimental Raw materials Microbrillar cellulose (MFC) was prepared by disintegration and homogenization of fully bleached spruce sulphite pulp from Borregaard ChemCell. Pulp bres were cut to an average length of approx. 1 mm and diluted to 1% consistency before homogeniziation in a Gaulin M12 homogenizer with a pressure drop of 600 bar at each pass. Details of the procedure are described elsewhere (Andresen et al. 2006). The substrate (base) paper was prepared from fully bleached softwood kraft pulp from Sodra Cell, Tofte, Norway. Preparation of test specimens Three series of samples were prepared; 1) lms of MFC having no orientation, 2) lms of oriented MFC prepared in a dynamic sheet former and 3) layers of MFC on substrate base paper, prepared by spraying of MFC suspensions on the paper, using the dynamic sheet former. (1) MFC lms were prepared by from an approximately 0.1% MFC suspension poured into a cylindrical mould. The bottom of the cylinder was a layered structure consisting of polyamide lter cloth, coarseness 235 mesh (top), a lter paper (middle) and a supporting Cu wire (bottom). The water was removed by free suction through the polyamide lm into the lter paper and drainage through the bottom as well as evaporation from the top. The mould was 6 cm in diameter, allowing for preparation of test pieces with dimensions 1.5 9 5 cm. The lm thicknesses were 2033 lm, corresponding to basis weights between 1530 g/m2 The lms were dried by evaporation at room temperature. They could be easily removed from the polyamide lter, without visible remnants of the MFC in the cloth. (2) Films of oriented MFC were prepared using a dynamic sheet former (FiberTech, Sweden) and two wires with coarseness 125 and 250 mesh. The

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77

headbox consistency was 0.06%. Using the 125 mesh wire the wire loss was 20%. The basis weights of the two types of lms thus produced were 24 and 16 g/m2. They were pressed (1 bar), using blotting paper on top of the lm during pressing. The lms were dried on a drum drier at 50 C. The wire was not removed until after drying. (3) MFC as a surface layer on paper. Oriented sheets were prepared using a dynamic sheet former (FiberTech, Sweden). The base paper was made from unbeaten softwood pulp. MFC was deposited on the top of the wet base paper in the dynamic sheet former. The top layer and the base paper were thus combined wet in wet. The extent to which this resulted in mixing of the MFC with bres was not investigated, but it has later been shown for lms prepared in the same way (Eriksen et al. 2008) that the mixing is negligible. The total basis weight of the sheets was in all cases 90 g/m2. The basis weights of the top layers were varied from 2 to 8 g/m2, i.e. the basis weight of the base paper varied between 88 and 82 g/m2. A reference sheet without any coating was also prepared. Oriented sheets coated with surface modied MFC were prepared using the same procedure. The MFC was in this case modied by grafting of amine (bis(3-aminopropyl)amine) on MFC surfaces modied with isocyanate, giving positively charged MFC, or of succinic anhydride, resulting in a higher negative charge of the bres by introduction of acid groups. Detailed descriptions of the modication procedures are given by Stenstad et al. (2008). The sheets were pressed and dried according to a standardised procedure (ISO 5269-1:1998). The wire side of the paper was in contact with a drying plate while the top side with the MFC layer was covered with blotting paper in the same way as in the preparation of oriented MFC sheets. Characterization The test specimens were analysed by measuring tensile strength and elongation (ISO 1924-2:1994), grammage (ISO 536:1995), thickness and density (ISO 534:1988). Six replicates were used for these measurements. Air permeability was assessed according to ISO 5636-5:2003 using three replicates. The tensile strength and elongation were measured with a Zwick material tester (T1-FRxxMOD.A1K, serial no.

119249, model 2005). Conditions in the test room were: relative humidity 50%, temperature 23 C. The E-modulus was calculated from the slope of a linear regression of the steepest part of the stress-strain curve of the MFC-lms. The oxygen permeability was measured according to the ASTM standard D3985 (23 C, 0% RH on the top side, 50% RH on the bottom side). The MFC lms were mounted in a cell where 100% O2 was ushed on the top side and 100% N2 on the bottom side. The amount of O2 transferred through the lms was assessed by a Mocon Coulox oxygen sensor in the N2 gas ow. Two replicates were measured for each sample. Surface characteristics were assessed by eldemission scanning electron microscopy, FEG-SEM. Platinum-coated samples were investigated with a Zeiss Gemini Supra 55VP FEG-SEM instrument. The images were acquired with a lateral secondary electron (SE) detector at 600009 magnication. The Inlens SE-detector capability of the FEG-SEM was used to obtain high resolution images at 1700009 magnication.

Results Strength properties The strength properties and permeability of the random MFC lms, the oriented MFC lms and the sheets with layers of MFC are shown in Tables 13 respectively. In order to facilitate comparison of results for the different types of sheets, selected results are also plotted in Figs. 17. The tensile indices of MFC lms, oriented MFC sheets and the paper sheets coated with MFC layers are compared in Fig. 1. The tensile indices of the MFC lms and sheets were considerably higher than typical tensile indices for paper, which are in the range of 10100 kNm/kg, depending on the type of paper (Fellers and Norman 1996). The difference was not just a result of differences in densities, as seen Fig. 2, which shows the tensile indices of MFC lms and sheets as a function of their densities. Although the densities of the oriented MFC lms were much lower than those of the lms of randomly dispersed MFC, the tensile indices were not much different.

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78 Table 1 Strength and permeability of MFC lms prepared by free drying Sample code A B C D Basis weight (g/m2) 17 1 23 1 30 1 35 3 Thickness (lm) 21 1 23 1 30 1 33 2 Density (kg/m3) 811 47 878 24 974 42 1069 70 Tensile index Tensile strength (Nm/g) (MPa) 129 16 126 23 136 14 146 18 104 126 136 154 Elongation (%) 5.3 1.0 5.4 1.5 8.0 0.8 8.6 1.6

Cellulose (2009) 16:7585

E modulus (GPa) 15.7 1.3 16.7 0.7 16.5 0.2 17.5 1.0

Air permeability (nm Pa-1 s-1) 13 2 92 11 10 1

Table 2 Strength and elongation of oriented lms of MF Sample code Wire mesh Basis weight (g/m2) Thickness (lm) Density (kg/m3) E modulus (GPa) Tensile index (Nm/g) MD E F 250 125 16 1 24 1 32 3 84 8 &500 &300 7.1 0.8 6.1 0.2 135 28 117 8 CD 102 9 84 3 Elongation (%) MD 6.0 1.3 3.6 0.5 CD 6.9 1.3 4.0 0.2

MD = Machine direction, CD = Cross direction. Values of the E modulus are in the MD

Table 3 Strength and permeability of paper sheets with MFC layers Sample code Grammage (g/m2) Total G H I J 88.9 89.0 91.3 89.6 MFC 0 2 4 8 150 5 167 5 171 9 163 6 593 532 535 549 Thickness (lm) Density (kg/m3) Tensile index (Nm/g) MD 35 1 33 1 37 2 40 2 CD 18 1 20 1 23 1 23 1 Elongation (%) MD 2.0 0.9 2.4 0.2 2.5 0.1 2.6 0.1 CD 1.4 1.1 2.5 0.2 2.8 0.2 (6.5 0.9) 104 (3.3 1.6) 104 (2.6 2.0) 103 360 30 Air permeability (nm Pa-1 s-1)

MD = Machine direction, CD = Cross direction

The thickness of the MFC lms ranged from 21 to 33 lm. The diameter of a typical Norwegian spruce bre (Picea abies) in wood is 30 10 lm (Fengel and Grosser 1976). Thus, the thickness of the MFC lms was in the same range as the thickness of a single bre. The elongation of the MFC lms ranged from 5.3 to 8.6% (Fig. 3), increasing with basis weight. The low elongation of the oriented sheet prepared on a 125 mesh wire was probably due to the removal of ne material from the suspension (20%). The elongation of the paper sheets, whether coated with MFC or not, was lower than that of the MFC lms, but increased when the thickness of the coating increased. Figure 4 shows the E-modulus of the MFC lms and oriented sheets. The E values increased continually as the basis weight increased. The E moduli of

the oriented sheets were much lower than those of the lms. This may be due to the use of thickness values in the calculations. If the densities are underestimated this will also give low values of the E modulus. Figure 5 shows the tensile stiffness of the same samples. In this case the data are normalized by the amount of material. The tensile stiffnesses are in the same range for all MFC lms. Finally, Fig. 6 shows the tensile index of the coated base paper as a function of the basis weight of the MFC layer. An increase in tensile index in both MD and CD as the thickness of the MFC layer increases was observed. The gure also shows results for sheets coated with lms of cationically and anionically modied MFC. There were no differences in strengths between the samples coated with pure MFC and to those with increased charges, whether positive or negative.

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180 160 140

79
12

10

Tensile index, Nm/g

120 100 80 60 40 20 0 0 5 10 15 20 25 30 35 40

Elongation, %
Basis weight, g/m2

0 0 5 10 15 20 25 30 35 40

Fig. 1 Tensile index as a function of grammage. j: MFC lms, u: oriented MFC lm, MD direction, 250 mesh, d: oriented MFC lm, MD direction, 125 mesh, s: tensile index of paper sheets coated with unmodied MFC, total grammage 90 1 g/m2, as a function of the grammage of the MFC coating, m: Reference paper sheet
180

Grammage, g/m2

Fig. 3 Elongation as a function of MFC grammage. d: MFC lms; j: oriented MFC sheet, MD, 250 mesh; h: oriented MFC sheet, MD, 125 mesh; s: paper sheets coated by 28 g/m2 MFC lm, total grammage 90 1 g/m2, u: reference sheet

20

160

18 16

Tensile index, Nm/g

E-modulus, GPa

140

14 12 10 8 6 4

120

100

80

2 0 0 5 10 15 20 25 30 35 40

60 0 0,2 0,4 0,6 0,8 1 1,2

Grammage, g/m2

Density, g/cm3

Fig. 2 Tensile index as a function of sheet density. j: MFC lms, u: Oriented MFC lm, MD direction, 250 mesh, d: Oriented MFC lm, MD direction, 125 mesh

Fig. 4 E-modulus as a function of grammage of MFC lms prepared by ltration (j); oriented MFC lms, 250 mesh, MD direction (u); oriented MFC lms, 125 mesh, MD direction (d)

Barrier properties The air permeability for base paper (the reference), MFC coated base paper and MFC lms are given in Tables 1, 3 and Fig. 7. The air permeability decreased upon coating with MFC and was further

reduced dramatically as the thickness of the MFC layer increased. A constant level of about 10 nm/Pa s was obtained for the MFC lms. Table 4 shows the oxygen transmission rate for two MFC lms compared with literature values for various synthetic polymers.

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80
25

Cellulose (2009) 16:7585

100000

Tensile stiffness (MNm/kg)

20

10000

15

Airperm. (nm/Pa s)
0 5 10 15 20 25 30 35 40

1000

10

100

10

1 0 10 20 30 40

Basis weight

(g/m2)

MFC basis weight (g/m2)

Fig. 5 Tensile stiffness as a function of basis weight of MFC lms (m), oriented sheet, 250 mesh (j) and oriented sheet, 125 mesh (s)
50 45

Fig. 7 Air permeabilities of the base paper (reference) (9), MFC coated base paper, total grammage 90 1 g/m2 (m) and MFC lms (u)

Tensile index (kNm/kg)

40 35 30 25 20 15 10 0 2 4 6 8 10

MFC layer (g/m2)

Fig. 6 Tensile index of oriented base paper coated with modied MFC as a function of the basis weight of the MFC layer. u: MD, reference, j: MD, unmodied MFC, m: MD, MFC modied with amine (cationic), d: MD, MFC modied with succinic anhydride (anionic), e: CD, reference, h: CD, unmodied MFC, D: CD, MFC modied with amine (cationic). s: CD, MFC modied with succinic anhydride (anionic). Note that some points overlap

Discussion Strength properties Tensile indices As noted above, the strengths of the MFC lms (tensile index 129146 Nm/g) are much higher than

those of paper. The tensile indices of paper usually range from 10 to 100 kNm/kg (Fellers and Norman 1996). The tensile strengths of the MFC lms (104 154 MPa) are comparable to the tensile strength of cellophane (125 MPa longitudinal, 75 MPa transversal) (Fink et al. 2001), but the E-moduli of the MFC lms are much higher (15.717.5 GPa vs. 3.7 5.4 GPa). This may be due to the higher stiffness of the crystalline cellulose brils in the MFC lms, compared to the amorphous structure of the cellulose in the cellophane lms. The densities of the lms of randomly oriented MFC range from 0.8 to 1,1 g/cm3, but the densities of the oriented lms, in particular the one prepared with a 125 mesh wire appear to be very low without any marked effect on the strength which remained constant within experimental error. For the 125 mesh sheet the wire loss was 20%. The material that was lost had probably very small dimensions, leaving a coarser material in the resulting lms. This may explain of the much lower densities of these sheets. The densities of the oriented lms may be underestimated if the surface roughness is large. Large surface roughness, due to e.g. wire mark, will lead to too high thickness values and thus underestimated densities. In any case, based on the results, the nest material does not seem to have played any important role for the strength properties. The thickness of the MFC lms was in the same range as the thickness of a single bre. In view of

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Cellulose (2009) 16:7585 Table 4 Permeabilities of MFC lms and literature values for lms of synthetic polymers and cellophane Sample Grammage (g/m2) Thickness (lm) Air permeability (nm/Pa s) Oxygen permeability in the material (ml m-2 day-1) 17.0, 18.5 17.0, 17.0 50130a 915a 35a 7800a 2600a 3b

81

MFC lm A MFC lm C Polyester, oriented Polyester, oriented, PVdC coated EVOH Polyethylene LD Polyethylene HD Cellophane
a b

17 1 29 1

21 1 30 1 25 25 25 25 25 21

13 2 11 3

Two measurements of oxygen permeability were made for each MFC sample; both results are given in the table Parry (1993) Kjellgren and Engstrom (2006)

this, the tensile index values must be considered remarkably high. The elongations of the MFC lms were high, ranging from 5.3 to 8.6%. The lms were free dried, which normally gives higher values for elongation compared to restricted drying. However, the elongation values for the oriented MFC lm prepared on 125 mesh wire under restricted conditions was 6.0% in MD and 6.9 in CD. The oriented lm produced with the coarser wire (sample F) had lower values, 3.6 and 4.0% in MD and CD respectively. According to Dodson and Herdman (1982) the elongation is a linear function of the shrinkage and the value of restricted drying (zero shrinkage) is independent of the manufacture process and orientation of the sheets. In addition, the elastic modulus, and thus also the elongation, depends on the basis weight up to a level of approx. 45 g/m2 for paper (Alava and Niskanen 2006). Thus, only samples with equal basis weight can be compared. Based on this, the elongations of samples E and F can be compared to samples A and B respectively, where sample E and F represent the elongation at no shrinkage while A and B correspond to lms with free drying. The values are however quite similar except for the MFC sheet produced with the coarser wire. As noted above, the brils with the smallest dimensions were probably lost during the sheet forming with this wire. Thus, it seems that the nest material played a role in the elongation. The relative importance of factors determining the elongation in a MFC lm may be different from

paper. A paper sheet has large porosity; in the bre wall due to the lumen and between the bres because they form a network. Each bril in MFC is solid without any pores. Their ability to swell and shrink is therefore limited. The elongation of cellophane lms is reported to be 2575% (Fink et al. 2001), which is considerably higher than that of MFC lms. However, these values are not directly comparable due to the different ways of preparation of the lms. E-modulus Figure 4 shows that the elastic modulus of MFC lms increased continually as the basis weight increased, never reaching a constant level. According to Alva and Niskanen (2006) the value of E of paper is usually constant from basis weight 45 g/m2 and upwards. The theoretical E-modulus of cellulose bres as a function of bril angle was calculated and compared to experimental results by Page et al. (1977). The theoretical E modulus was 80 GPa at zero bril angle and decreased to 1718 GPa at a bril angle of 50. The experimental values were a little lower. The MFC lms are composed of brils that are randomly oriented. The obtained values, 15.717.5 GPa, are in the same range as for bres with low bril angle. According to Cox (1952) the E-modulus of a random network of ideal straight and innite bres is one third of the E-modulus of the individual bres. The maximal theoretical value is according to this 1/3 80 & 27 GPa. For bril

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networks that deviate from the ideal situation the values will be lower. For paper the values are typically 5 GPa (Alava and Niskanen 2006). Surface layer of MFC on base paper Comparison of the tensile indexes of the base paper with the MFC layer and MFC lms (Fig. 1) shows that there is a large difference between the coated samples and the pure MFC samples. The strengthincreasing potential of the MFC layer seems not to be fully utilized. An explanation for this may be seen in Figs. 8 and 9. Figure 8 shows a pure MFC lm in two magnications. A smooth, continuous lm is observed. Figure 9 shows the base paper without and with the MFC coating. The bres in the base paper are clearly visible through the MFC layer. In addition, the surface of the MFC layer has signs of disorder and discontinuities. This will most probably reduce the strength. By optimizing the technique for manufacture of coated sheets, it may be possible to obtain a larger strength increase and utilize the potential in the MFC layer better. The elongation of the sheets with a layer of MFC was about 2.5%, which is lower than elongation of the pure MFC lms, 5.38.6% (see Table 3 and Fig. 3). When the sheets are exposed to a tensile force, the least extensible part of the sheet will break rst. The whole load must then be carried by the other parts of the sheet. This will make the strength of a layered sheet poorer than a linear combination of the strength of the two layers.

The results showed that layer of anionic or cationic MFC gave the same strength as unmodied MFC. This indicates that the hydrogen bonds between the brils give equally strong bonds between MFC brils with increased surface charge. Barrier properties The very low air permeability of the lms implies that there were no connected pores through the whole cross section of the lms. It was therefore of interest to measure the oxygen transmission rate (OTR). When there are no pores allowing for gas ow through a material, the gas permeability will depend on the dissolution of oxygen and its rate of diffusion in the particular material. In Table 4 values of the OTR for two MFC lms are compared to literature values of various synthetic polymers. The values for the MFC lms are 17.0 and 17.8 ml m-2 day-1. The recommended OTR for modied atmosphere packaging is below 1020 ml m-2 day-1 (Parry 1993). Indeed, lms manufactured from pure MFC without any additions full this requirement. Compared to lms made from synthetic polymers and with approximately the same thickness, the MFC lms studied here were competitive with the best synthetic polymers with respect to oxygen transmission rate (PVdC coated, oriented polyester and EVOH). The explanation for the good barrier properties is probably that low permeability of cellulose generally is enhanced with the crystalline structure of the brils. Commercial cellophane lms

Fig. 8 MFC lm in two magnications

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Fig. 9 (Upper left) Base paper. (Upper right and lower images) Base paper coated with 8 g/m2 MFC in three magnications

with thickness of 20.8 lm are reported to have OTR & 3 ml m-2 day-1 (Kjellgren and Engstrom 2006). The role of the crystalline structure of plastics is discussed by Lagaron et al. (2004) where it is emphasized that high crystallinity improves barrier properties. A composite material of high density polyethylene and cellulose showed very good barrier properties towards oxygen. This was explained by the presence of impermeable cellulose crystals (Fendler et al. 2007). However, it should be noted that permeability measurements may be inuenced by the tendency of cellulose surfaces to adsorb water molecules. For example, it has been found that the oxygen permeability of cellophane increases by a factor 20 when RH increases from 0 to 50% (Krochta et al. 1994). The effect of RH on permeability of MFC lms would warrant further investigation.

Conclusions MFC produced from spruce sulphite bres can be used to prepare lms with high strength properties and to improve the strength properties of paper by application of thin layers of MFC. The strength properties of MFC lms are comparable to or higher than those of cellophane, but the E-modulus of MFC lms is higher. This may be explained by the high degree of crystallinity of the brils in the MFC lms. No signicant differences were observed between native MFC and MFC with increased surface charge, whether positive or negative. Thus, the inter-brillar hydrogen bonds seem to be of predominating importance in spite of the additional surface charge. The E modulus of a lm composed of randomly oriented brils with thickness in the same range as the thickness of a single spruce bre, is

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Cellulose (2009) 16:7585 Dodson CTJ, Herdman PT (1982) Mechanical properties of paper. In: Rance HF (ed) Handbook of paper science 2, the structural and physical properties of paper. Elsevier, Amsterdam, pp 108109 Dufresne A, Cavaille J-Y, Vignon MR (1998) Mechanical behaviour of sheets prepared from sugar beet cellulose microbrils. J Appl Polym Sci 64(6):11851194. doi:10.1002/(SICI)1097-4628(19970509)64:6\1185::AIDAPP19[3.0.CO;2-V Eriksen , Gregersen W, Syverud K (2008) The effect of MFC on handsheet surface and printing properties. In: Proceedings, progress in paper physics seminar, June 25, Espoo, Finland Fellers C, Norman B (1996) Pappersteknik. Avdelingen for Pappersteknik, Kungl Tekniska Hogskolan, Stockholm. ISBN: 91-7170-741-7, TABS-Tryckeri AB i Smaland, 292 pp Fendler A, Villanueva MP, Giminez E, Lagaron JM (2007) Characterization of the barrier properties of composites of HDPE and puried cellulose bres. Cellulose 14:427 438. doi:10.1007/s10570-007-9136-x Fengel D, Grosser D (1976) Holz, Morphologie und Eigens chaften. In: Ullmanns Encyklopadie der technischen Chemie, 4th edn, vol 12. Verlag Chemie, Weinheim, pp 669679 Fink H-P, Weigel P, Purz HJ, Ganster J (2001) Structure formation of regenerated cellulose materials from NMMOsolutions. Prog Polym Sci 26:14731524. doi:10.1016/ S0079-6700(01)00025-9 Henriksson M, Berglund L (2007) Structure and properties of cellulose nanocomposite lms containing melamine formaldehyde. J Appl Polym Sci 106:28172824. doi:10.1002/ app.26946 Khopade AJ, Jain NK (1990) A stable multiple emulsion system bearing isoniazid: preparation and characterization. Drug Dev Ind Pharm 24(3):289293. doi:10.3109/0363 9049809085622 Kjellgren H, Engstrom G (2006) Inuence of base paper on the barrier properties of chitosan-coated paper. Nordic Pulp Pap Res J 21(5):685689. doi:10.3183/NPPRJ-2006-2105-p685-689 Krochta JM, Baldwin EA, Nisperos-Carriedo MO (eds) (1994) Edible coatings and lms to improve food quality. TECHNOMIC Publishing, Lancaster Lagaron JM, Catala R, Gavara R (2004) Structural characteristics dening high barrier properties in polymeric materials. Mater Sci Technol 20:17. doi:10.1179/02670 8304225010442 Lopez-Rubio A, Lagaron JM, Ankerfors M, Lindstrom T, Nordqvist D, Mattozzi A et al (2007) Enhanced lm forming and lm properties of amylopectin using microbrillated cellulose. Carbohydr Polym 68(4):718727. doi:10.1016/j.carbpol.2006.08.008 Malainine ME, Mahrouz M, Dufresne A (2005) Thermoplastic nanocomposites based on cellulose microbrils from Opuntia cus-indica parenchyma cell. Compos Sci Technol 65:15201526. doi:10.1016/j.compscitech.2005.01.003 Nakagaito AN, Yano H (2005) Novel high-strength biocomposites based on microbrillated cellulose having nanoorder-unit web-like network structure. Appl Phys A 80: 155159. doi:10.1007/s00339-003-2225-2

comparable to values for cellulose bres with bril angle 50. The dense structure formed by the brils gives superior barrier properties. MFC lms with thicknesses of 2130 lm fulll the requirements for oxygen transmission rate in modied atmosphere packaging and are comparable to the best synthetic polymers, like PVdC coated oriented polyester. The strength of base paper increases signicantly upon coverage with a layer of less than 10% MFC, whether pure or surface modied, and the air permeability decreases dramatically. The reduced surface porosity induced by brils explains the improved barrier properties. The reduced surface porosity may also be benecial for printing properties. The results indicate that MFC may contribute to broadening the applicability of cellulose-based packaging.
Acknowledgements The authors gratefully acknowledge Sodra Cell, Borregaard Industries, Akzo Nobel and the NANOMAT programme of the Research Council of Norway for funding. Olav Solheim (PFI) is thanked for data processing and yvind Gregersen (NTNU) and yvind Eriksen for valuable discussions. Per Olav Johnsen is acknowledged for acquiring the images.

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