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Cellulose (2009) 16:75–85 DOI 10.1007/s10570-008-9244-2

Strength and barrier properties of MFC films

Kristin Syverud Æ 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 microfibrillar cellulose (MFC) films by filtration on a polyamide filter 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 films formed by MFC isgiven.Typically,aMFCfilmwithbasisweight35 g/m 2 had tensile index 146 ± 18 Nm/g and elongation 8.6 ± 1.6%. The E modulus (17.5 ± 1.0 GPa) of a film composed of randomly oriented fibrils was comparable to values for cellulose fibres with a fibril angle of 50 . The strength of the films formed in the dynamic sheet former wascomparabletothestrengthoftheMFCfilmsprepared by filtration. The use of MFC as surface layer (0–8% of total basis weight) on base paper increased the strength of the paper sheets significantly 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 fibrils resulted in superior barrier properties. Oxygen transmission rates (OTR) as low as 17 ml m -2 day -1 were obtained for films prepared from pure MFC. This result fulfils the requirements for oxygen transmission rate in modified atmosphere packaging.

K. Syverud ( & )

Paper and Fibre Research Institute (PFI), Høgskoleringen 6b, NO-7491 Trondheim, Norway e-mail: kristin.syverud@pfi.no

P. Stenius

Ugelstad Laboratory, Department of Chemical Engineering, NTNU, Høgskoleringen 6b, NO-7491 Trondheim, Norway

Keywords

Microfibrillar cellulose Nano cellulose Paper

MFC Strength Barrier MFC films

Introduction

The production of microfibrillar cellulose (MFC hereafter) from wood fibres was demonstrated by Turbak et al. (1983) in the early 1980s. The smaller dimensions and the large surface area of MFC compared to fibres open up for new, perhaps unfore- seen possibilities to utilise cellulose-based materials. However, so far profitable production of MFC has been restricted by high energy consumption, difficul- ties 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. Pa¨a¨kko¨ 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; Lo´pez-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 films (Andresen et al. 2007). However, little has been reported about

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the use of MFC in paper applications or the properties of pure MFC films.

microfibrils from wood cellulose fibres. The use of pure MFC and MFC as a layer on base paper in order

The decomposition of wood fibres into micro- or

to

increase barrier properties are demonstrated.

nanofibrillar cellulose gives a material which retains many of the advantageous properties of cellulose fibres, such as the ability to form hydrogen bonds,

Experimental

resulting in a strong network. Taniguchi (1998) reports that the tensile strength of a MFC film from

Raw materials

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 films and paper are not specified. Production of MFC films is also described by Dufresne et al. (1998). They use MFC produced from sugar beet pulps and study the influence of pectins on mechanical properties. Hen- riksson and Berglund (2007) report an E modulus of 14 GPa for pure MFC films and E = 16.6 GPa for

Microfibrillar cellulose (MFC) was prepared by disintegration and homogenization of fully bleached spruce sulphite pulp from Borregaard ChemCell. Pulp fibres were cut to an average length of approx. 1 mm and diluted to 1% consistency before homog- eniziation 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.

composite films of MFC and melamine formaldehyde

2006).

(MF) containing 9% MF. Petrochemically based polymers predominate in packaging of foods due to their ease of processing,

The substrate (base) paper was prepared from fully bleached softwood kraft pulp from So¨dra Cell, Tofte, Norway.

excellent water barrier properties and low cost. However, there is an increasing interest in replacing

Preparation of test specimens

synthetic polymers with more sustainable materials. The barrier properties of plastics are low in compar- ison to traditional packaging materials, such as glass and hermetics. Hence, polymer films with low permeability to low molecular gases, such as O 2 and CO 2 , have been developed. Such polymers are used in connection with modified atmosphere pack-

Three series of samples were prepared; 1) films of MFC having no orientation, 2) films 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.

aging (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 poly- ethylene (PE). The crystallinity of the polymers is of

(1) MFC films were prepared by from an approx- imately 0.1% MFC suspension poured into a cylindrical mould. The bottom of the cylinder was a layered structure consisting of polyamide filter cloth, coarseness 235 mesh (top), a filter paper (middle) and

large importance for the barrier properties of the

a

supporting Cu wire (bottom). The water was

polymers (Lagaron et al. 2004).

removed by free suction through the polyamide film

The MFC fibrils have dimensions in the nano-

into the filter paper and drainage through the bottom

scale, ranging upwards from less than 10 nm in

as

well as evaporation from the top. The mould was

diameter. It is well known that it is difficult for other molecules to penetrate the crystalline parts of cellu- lose fibrils. These properties, in combination with the ability of the dried fibrils to form a dense network held together by strong inter-fibrillar bonds, suggest that due to the barrier and strength properties of the films, 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 films prepared from

6 cm in diameter, allowing for preparation of test pieces with dimensions 1.5 9 5 cm. The film thick- nesses were 20–33 lm, corresponding to basis weights between 15–30 g/m 2 The films were dried by evaporation at room temperature. They could be easily removed from the polyamide filter, 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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Cellulose (2009) 16:75–85

77

headbox consistency was 0.06%. Using the 125 mesh wire the wire loss was 20%. The basis weights of the two types of films thus produced were 24 and 16 g/m 2 . They were pressed (1 bar), using blotting paper on top of the film during pressing. The films 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 fibres was not investigated, but it has later been shown for films 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/m 2 . The basis weights of the top layers were varied from 2 to 8 g/m 2 , i.e. the basis weight of the base paper varied between 88 and 82 g/m 2 . A reference sheet without any coating was also prepared.

Characterization

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-films. 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 films were mounted in a cell where 100% O 2 was flushed on the top side and 100% N 2 on the bottom side. The amount of O 2 transferred through the films was assessed by a Mocon Coulox oxygen sensor in the N 2 gas flow. Two replicates were measured for each sample. Surface characteristics were assessed by field- emission 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 magnification. The Inlens SE-detector capability of the FEG-SEM was used to obtain high resolution images at 1700009 magnification.

Oriented sheets coated with surface modified MFC were prepared using the same procedure. The MFC was in this case modified by grafting of amine (bis-

Results

(3-aminopropyl)amine) on MFC surfaces modified with isocyanate, giving positively charged MFC, or

Strength properties

of succinic anhydride, resulting in a higher negative charge of the fibres by introduction of acid groups. Detailed descriptions of the modification 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.

The strength properties and permeability of the random MFC films, the oriented MFC films 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 films, oriented MFC sheets and the paper sheets coated with MFC layers are compared in Fig. 1. The tensile indices of the MFC films and sheets were considerably higher than

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 accord- ing 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.

typical tensile indices for paper, which are in the range of 10–100 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 films and sheets as a function of their densities. Although the densities of the oriented MFC films were much lower than those of the films of randomly dispersed MFC, the tensile indices were not much different.

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Cellulose (2009) 16:75–85

Table 1

Strength and permeability of MFC films prepared by free drying

 

Sample

Basis weight

Thickness

Density

Tensile index

Tensile strength

Elongation

E modulus

Air permeability (nm Pa -1 s -1 )

code

(g/m 2 )

(lm)

(kg/m 3 )

(Nm/g)

(MPa)

(%)

(GPa)

A

17 ± 1

21 ± 1

811 ± 47

129 ± 16

104

5.3 ± 1.0

15.7 ± 1.3

13 ± 2

B

23 ± 1

23 ± 1

878 ± 24

126 ± 23

126

5.4 ± 1.5

16.7 ± 0.7

9 ± 2

C

30 ± 1

30 ± 1

974 ± 42

136 ± 14

136

8.0 ± 0.8

16.5 ± 0.2

11

D

35 ± 3

33 ± 2

1069 ± 70

146 ± 18

154

8.6 ± 1.6

17.5 ± 1.0

10 ± 1

Table 2

Strength and elongation of oriented films of MF

 

Sample code

Wire

Basis weight (g/m 2 )

Thickness

(lm)

Density (kg/m 3 )

E modulus

Tensile index

Elongation (%)

 

mesh

(GPa)

(Nm/g)

 

MD

CD

MD

CD

E

250

16 ± 1

32 ± 3

&500

7.1 ± 0.8

135 ± 28

102 ± 9

6.0 ± 1.3

6.9 ± 1.3

F

125

24 ± 1

84 ± 8

&300

6.1 ± 0.2

117 ± 8

84 ± 3

3.6 ± 0.5

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/m 2 )

Thickness (lm)

Density (kg/m 3 )

Tensile index

Elongation (%)

Air permeability (nm Pa -1 s -1 )

 

(Nm/g)

Total

MFC

MD

CD

MD

CD

G

88.9

0

150 ± 5

593

35 ± 1

18 ± 1

2.0 ± 0.9

(6.5 ± 0.9) 10 4

H

89.0

2

167 ± 5

532

33 ± 1

20 ± 1

2.4 ± 0.2

1.4 ± 1.1

(3.3 ± 1.6) 10 4

I

91.3

4

171 ± 9

535

37 ± 2

23 ± 1

2.5 ± 0.1

2.5 ± 0.2

(2.6 ± 2.0) 10 3

J

89.6

8

163 ± 6

549

40 ± 2

23 ± 1

2.6 ± 0.1

2.8 ± 0.2

360 ± 30

MD

= Machine direction, CD = Cross direction

 

The thickness of the MFC films ranged from 21 to 33 lm. The diameter of a typical Norwegian spruce fibre (Picea abies) in wood is 30 ± 10 lm (Fengel and Grosser 1976). Thus, the thickness of the MFC films was in the same range as the thickness of a single fibre. The elongation of the MFC films 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 fine material from the suspension (20%). The elon- gation of the paper sheets, whether coated with MFC or not, was lower than that of the MFC films, but increased when the thickness of the coating increased. Figure 4 shows the E-modulus of the MFC films and oriented sheets. The E values increased contin- ually as the basis weight increased. The E moduli of

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the oriented sheets were much lower than those of the films. 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 films.

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 figure also shows results for sheets coated with films of cationically and anionically modified MFC. There were no differences in strengths between the samples coated with pure MFC and to those with increased charges, whether positive or negative.

Cellulose (2009) 16:75–85

79

180 160 140 120 100 80 60 40 20 0 0 5 10 15 20
180
160
140
120
100
80
60
40
20
0
0
5
10
15
20
25
30
35
40
Tensile index, Nm/g

Basis weight, g/m 2

Fig. 1 Tensile index as a function of grammage. j: MFC films, u: oriented MFC film, MD direction, 250 mesh, d :

oriented MFC film, MD direction, 125 mesh, s: tensile index of paper sheets coated with unmodified MFC, total grammage 90 ± 1 g/m 2 , as a function of the grammage of the MFC coating, m : Reference paper sheet

180 160 140 120 100 80 60 0 0,2 0,4 0,6 0,8 1 1,2 Tensile
180
160
140
120
100
80
60
0
0,2
0,4
0,6
0,8
1
1,2
Tensile index, Nm/g

Density, g/cm 3

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

Oriented MFC film, MD direction, 125 mesh

Barrier properties

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

12 10 8 6 4 2 0 0 5 10 15 20 25 30 35
12
10
8
6
4
2
0
0
5
10
15
20
25
30
35
40
Elongation, %

Grammage, g/m 2

Fig. 3 Elongation as a function of MFC grammage. d : MFC films; j: oriented MFC sheet, MD, 250 mesh; h : oriented MFC

sheet, MD, 125 mesh; s : paper sheets coated by 2–8 g/m 2 MFC

film, total grammage 90 ± 1 g/m 2 , u : reference sheet

20 18 16 14 12 10 8 6 4 2 0 0 5 10 15
20
18
16
14
12
10
8
6
4
2
0
0
5
10
15
20
25
30
35
40
E-modulus, GPa

Grammage, g/m 2

Fig. 4 E-modulus as a function of grammage of MFC films

prepared by filtration ( j ); oriented MFC films, 250 mesh,

MD direction ( u); oriented MFC films, 125 mesh, MD

direction (d )

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

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25 20 15 10 5 0 0 5 10 15 20 25 30 35 40
25
20
15
10
5
0
0
5
10
15
20
25
30
35
40
Tensile stiffness (MNm/kg)

Basis weight (g/m 2 )

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

50 45 40 35 30 25 20 15 10 0 2 4 6 8 10
50
45
40
35
30
25
20
15
10
0
2
4
6
8
10
Tensile index (kNm/kg)

MFC layer (g/m 2 )

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

Discussion

Strength properties

Tensile indices

As noted above, the strengths of the MFC films (tensile index 129–146 Nm/g) are much higher than

123

100000 10000 1000 100 10 1 0 10 20 30 40 Airperm. (nm/Pa s)
100000
10000
1000
100
10
1
0
10
20
30
40
Airperm. (nm/Pa s)

MFC basis weight (g/m 2 )

Fig. 7 Air permeabilities of the base paper (reference) (9), MFC coated base paper, total grammage 90 ± 1 g/m 2 ( m ) and MFC films ( u)

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 films (104– 154 MPa) are comparable to the tensile strength of cellophane (125 MPa longitudinal, 75 MPa transver- sal) (Fink et al. 2001), but the E-moduli of the MFC films are much higher (15.7–17.5 GPa vs. 3.7– 5.4 GPa). This may be due to the higher stiffness of the crystalline cellulose fibrils in the MFC films, compared to the amorphous structure of the cellulose in the cellophane films. The densities of the films of randomly oriented MFC range from 0.8 to 1,1 g/cm 3 , but the densities of the oriented films, 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 films. This may explain of the much lower densities of these sheets. The densities of the oriented films may be underes- timated 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 finest material does not seem to have played any important role for the strength properties. The thickness of the MFC films was in the same range as the thickness of a single fibre. In view of

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Table 4

Permeabilities of MFC films and literature values for films of synthetic polymers and cellophane

 

Sample

Grammage (g/m 2 )

Thickness

Air permeability

Oxygen permeability in the material (ml m -2 day -1 )

(lm)

(nm/Pa s)

MFC film A

17 ± 1

21 ± 1

13 ± 2

17.0, 18.5

MFC film C

29 ± 1

30 ± 1

11 ± 3

17.0, 17.0

Polyester, oriented

25

50–130 a

Polyester, oriented,

25

9–15 a

PVdC coated

EVOH

25

3–5 a

Polyethylene LD

25

7800

a

Polyethylene HD

25

2600

a

Cellophane

21

3 b

Two measurements of oxygen permeability were made for each MFC sample; both results are given in the table

a Parry (1993)

b Kjellgren and Engstro¨m (2006)

this, the tensile index values must be considered remarkably high. The elongations of the MFC films were high, ranging from 5.3 to 8.6%. The films were free dried, which normally gives higher values for elongation compared to restricted drying. However, the elonga- tion values for the oriented MFC film prepared on 125 mesh wire under restricted conditions was 6.0% in MD and 6.9 in CD. The oriented film 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/m 2 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 films with free drying. The values are however quite similar except for the MFC sheet produced with the coarser wire. As noted above, the fibrils with the smallest dimensions were probably lost during the sheet forming with this wire. Thus, it seems that the finest material played a role in the elongation. The relative importance of factors determining the elongation in a MFC film may be different from

paper. A paper sheet has large porosity; in the fibre wall due to the lumen and between the fibres because they form a network. Each fibril in MFC is solid without any pores. Their ability to swell and shrink is therefore limited. The elongation of cellophane films is reported to be 25–75% (Fink et al. 2001), which is considerably higher than that of MFC films. However, these values are not directly comparable due to the different ways of preparation of the films.

E-modulus

Figure 4 shows that the elastic modulus of MFC films 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/m 2 and upwards. The theoretical E-modulus of cellulose fibres as a function of fibril angle was calculated and compared to exper- imental results by Page et al. (1977). The theoretical E modulus was 80 GPa at zero fibril angle and decreased to 17–18 GPa at a fibril angle of 50 . The experimental values were a little lower. The MFC films are composed of fibrils that are randomly oriented. The obtained values, 15.7–17.5 GPa, are in the same range as for fibres with low fibril angle. According to Cox (1952) the E-modulus of a random network of ideal straight and infinite fibres is one third of the E-modulus of the individual fibres. The maximal theoretical value is according to this 1/3 80 & 27 GPa. For fibril

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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 films (Fig. 1) shows that there is a large difference between the coated samples and the pure MFC samples. The strength- increasing 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 film in two magnifications. A smooth, continuous film is observed. Figure 9 shows the base paper without and with the MFC coating. The fibres 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 films, 5.3–8.6% (see Table 3 and Fig. 3). When the sheets are exposed to a tensile force, the least extensible part of the sheet will break first. 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 unmodified MFC. This indicates that the hydrogen bonds between the fibrils give equally strong bonds between MFC fibrils with increased surface charge.

Barrier properties

The very low air permeability of the films implies that there were no connected pores through the whole cross section of the films. It was therefore of interest to measure the oxygen transmission rate (OTR). When there are no pores allowing for gas flow 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 films are compared to literature values of various synthetic polymers. The values for the MFC films are 17.0 and 17.8 ml m -2 day -1 . The recommended OTR for modified atmosphere packaging is below 10–20 ml m -2 day -1 (Parry 1993). Indeed, films manufactured from pure MFC without any additions fulfil this requirement. Compared to films made from synthetic polymers and with approximately the same thickness, the MFC films 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 fibrils. Commercial cellophane films

with the crystalline structure of the fibrils. Commercial cellophane films Fig. 8 MFC film in two

Fig. 8

MFC film in two magnifications

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Cellulose (2009) 16:75–85

83

Cellulose (2009) 16:75–85 83 Fig. 9 ( Upper left ) Base paper. ( Upper right and

Fig. 9

(Upper left) Base paper. (Upper right and lower images) Base paper coated with 8 g/m 2 MFC in three magnifications

with thickness of 20.8 lm are reported to have OTR & 3 ml m -2 day -1 (Kjellgren and Engstro¨m 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 influenced by the tendency of cellulose surfaces to adsorb water molecules. For example, it has been found that the oxygen perme- ability 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 films would warrant further investigation.

Conclusions

MFC produced from spruce sulphite fibres can be used to prepare films with high strength properties and to improve the strength properties of paper by application of thin layers of MFC. The strength properties of MFC films are comparable to or higher than those of cellophane, but the E-modulus of MFC films is higher. This may be explained by the high degree of crystallinity of the fibrils in the MFC films. No significant differences were observed between native MFC and MFC with increased surface charge, whether positive or negative. Thus, the inter-fibrillar hydrogen bonds seem to be of predominating impor- tance in spite of the additional surface charge. The E modulus of a film composed of ran- domly oriented fibrils with thickness in the same range as the thickness of a single spruce fibre, is

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Cellulose (2009) 16:75–85

comparable to values for cellulose fibres with fibril angle 50 . The dense structure formed by the fibrils gives superior barrier properties. MFC films with thick- nesses of 21–30 lm fulfill the requirements for oxygen transmission rate in modified atmosphere packaging and are comparable to the best synthetic polymers, like PVdC coated oriented polyester. The strength of base paper increases significantly upon coverage with a layer of less than 10% MFC, whether pure or surface modified, and the air perme- ability decreases dramatically. The reduced surface porosity induced by fibrils explains the improved barrier properties. The reduced surface porosity may also be beneficial for printing properties. The results indicate that MFC may contribute to broadening the applicability of cellulose-based packaging.

Acknowledgements The authors gratefully acknowledge So¨dra 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 Øyvind Gregersen (NTNU) and Øyvind Eriksen for valuable discussions. Per Olav Johnsen is acknowledged for acquiring the images.

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