[0001] The present disclosure relates to the production of sheets comprising fibrillated cellulose.

BACKGROUND

[0002] Recent advances in science and technology has created an environmental consciousness that shifted the societal and industrial focus towards green products and sustainable processes. This new approach was further fuelled by the scarcity of oil reserves, which gave an incentive to replace oil-based polymeric materials with the renewable and biodegradable materials. On the other hand, considering the fact that it was the excellent material properties and good processability of oil-based polymeric materials that established their market position, it is foreseeable that completely replacing these materials with their natural counterparts will not be an easy task.

[0003] Good barrier properties and processability, together with resistance to different environments and transparency are just some of the desired qualities for commonly used packaging materials, and oil-based polymeric materials indeed provide these qualities to a sufficient extent. To replace oil-based materials with renewable and bio-based materials, it is desirable to reach at least similar performance levels, and at a similar cost. One way to readily achieve this goal is to use naturally abundant polymers with existing industrially established large-scale production and processing protocols.

In this respect, packaging grade papers are very promising candidates to facilitate this transformation from non-renewable to renewable while keeping a similar cost, since it is made of naturally occurring cellulose-rich fibres in already existing processes in the pulp and paper industry.

[0004] Besides being one of the most abundant biopolymers on Earth, cellulose attracts considerable attention due to its high strength and stiffness combined with features like low weight, biodegradability and renewability. One of the promising new material streams of cellulose is the production and use of cellulose nanofibrils (CNFs) prepared from wood biomass. CNFs have desired properties, such as high aspect ratio and small dimensions, which not only enables strong and transparent barrier films for applications such as packaging, but also allows for an advanced bottom-up engineering of complex materials. Aside from its small size, an important feature of CNFs is their hydrophilicity, which is a great advantage for processing in aqueous media. However, this affinity for water combined with the small size of CNFs is also the reason for very long dewatering times, or energy demanding evaporation protocols, which to a large extent is what inhibits the feasible production of dry CNF-based materials on an industrial scale. In general, smaller fibre dimensions lead to better properties at the expense of longer processing times, which limits commercialization of nanocellulosic materials to a great extent.

SUMMARY

[0005] An object of the present disclosure is to overcome problems of the prior art.

[0006] There is thus, as a first aspect of the present disclosure, provided a method of producing a sheet comprising fibrillated cellulose, comprising the steps of:

a) providing chemically modified cellulose fibres in which a chargeable

moiety has been introduced and the C ₂ -C ₃ bond has been broken in at least part of the D-glucose units, wherein the charge density measured according to SCAN-CM 65:02 is 150-1500 meq/g;

a) forming a fibre web by dewatering a slurry comprising the modified

cellulose fibres; and

b) adding a base to the fibre web so as to obtain the sheet comprising fibrillated cellulose.

[0007] There is also provided, as a second aspect of the present disclosure, a method of producing a fibre web, comprising the steps of:

I. providing chemically modified cellulose fibres in which a chargeable

moiety has been introduced and the C ₂ -C ₃ bond has been broken in at least part of the D-glucose units, wherein the charge density measured according to SCAN-CM 65:02 is 150-1500 meq/g;

II. applying a slurry comprising the modified fibres to a forming wire of a paper machine;

III. dewatering the slurry on the forming wire of the paper machine to form a fibre web;

IV. further dewatering the fibre web in a press section of the paper machine; and V. drying the fibre web from the press section in a drying section of the paper machine to a density of o.8-1.8 g/cm ³ , such as 1.0-1.6 g/cm ³ .

[0008] The chemical modifications of the present disclosure allow for use of conventional papermaking methods in combination with a simple pH modification to achieve fibrillation on an already formed fibre web/paper. Delaying the fibrillation of the fibres until after sheet forming effectively eliminates or at least reduces the disadvantage of long dewatering times, while a“nanopaper” having advantageous properties is still obtained.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Aspects and embodiments are now described, by way of example, with refer- ence to the accompanying drawings, in which:

[0010] Fig. 1 shows the reaction scheme of (i) oxidation of C ₆ to introduce a carboxyl group, followed by (ii) periodate oxidation of the secondary alcohols in positions C ₂ and C ₃ to introduce two vicinal aldehydes.

[0011] Fig. 2 shows the level of fibrillation of modified fibres with respect to pH.

DETAILED DESCRIPTION

[0012] As a first aspect of the present disclosure, there is provided a method of producing a sheet comprising fibrillated cellulose. The method comprises the step of:

a) providing chemically modified cellulose fibres in which a chargeable

moiety has been introduced and the C ₂ -C ₃ bond has been broken in at least part of the D-glucose units, wherein the charge density measured according to SCAN-CM 65:02 is 150-1500 meq/g.

[0013] In a preferred embodiment, the C ₂ -C ₃ bond has been broken to form a dialdehyde.

[0014] The method may further comprise a pre-step of chemically modifying cellulose fibres to introduce the chargeable moiety and break the C ₂ -C ₃ bond in at least part of the D-glucose units and thereby obtain the modified cellulose fibres provided in step a).

[0015] Charge density is measured by conductometric titration according to SCAN- CM 65:02. [0016] The cellulose fibres are preferably never dried fibres. Further, the fibres are preferably bleached fibres, such as bleached fibres from chemical pulping, e.g. Kraft pulping (“bleached kraft fibres”). The origin of the fibres is normally wood.

[0017] Whether the chargeable moiety is introduced before or after the breakage of the C ₂ -C ₃ bond may depend on the chemistries used, e.g. in the pre-step. To avoid premature fibrillation, it is preferred that the reaction carried out last is not carried out at high pH, i.e. > pH 9. This means that if the introduction of the chargeable moiety is achieved by TEMPO oxidation at pH 10.5 (as in Example la below), it is preferably carried out before the breakage of the C2-C3 bond.

[0018] A periodate oxidation is a preferred way of breaking the C2-C3 bond. A periodate oxidation forms a dialdehyde (see Fig. 1). The periodate oxidation can be performed at room temperature, which gives a higher yield, and hence a higher charge, and carbonyl contents up to 8 mmol/g can be introduced without causing premature fibrillation. The periodate oxidation can also be performed at elevated temperature, such as 60 °C or 70 °C, which shortens the reaction time.

[0019] Examples of chemical reactions that introduce the chargeable moiety are

TEMPO oxidation, chlorite oxidation, carboxymethylation, phosphorylation and sulfonation. The chlorite oxidation act on aldehydes and is therefore carried out subsequent to periodate oxidation. TEMPO oxidation, carboxymethylation,

phosphorylation and sulfonation may be carried out before or after the periodate oxidation. It may however be preferred to carry out such chemistries before the periodate oxidation to ensure an aldehyde content in the final product.

[0020] Preferably the modified cellulose fibres provided in step a) have a charge density of 150-900 meq/g (i.e. 150-900 mmol/g of chargeable functional groups), such as 200-900 meq/g, such as 250-700 meq/g. The carbonyl content of the modified cellulose fibres maybe 1.0-7.0 mmol/g, such as 1.5-6.0 mmol/g, such as 1.5-5.0 mmol/g, such as 1.5-4.0 mmol/g. A drawback of a high conversion to carbonyls (i.e. breakage of a high proportion of the C2-C3 bonds) may be a low yield of product. Carbonyl content is measured according to a protocol based on Zhao et al. (Determination of degree of substitution of formyl groups in polyaldehyde dextran by the hydroxylamine

hydrochloride method. Pharm. Res. 8:400-402 (1991)). Fibres (approximately 0.3 g (dry basis)) were suspended in water (75 ml) and the pH was adjusted to pH 4. Then, hydroxylamine hydrochloride solution (75 ml, 0.25 M) was adjusted to pH 4 and mixed together with the fibre suspension. The mixture was allowed to react for 2 h before the fibres were separated from the solution by filtration using a pre-weighed filter paper. The exact mass of the fibres was then determined by oven-drying of the filter paper and the carbonyl amount was determined by titration back to pH 4 with sodium hydroxide (0.10 M). Two to three independent oxidations were performed at each oxidation time, and each reaction with hydroxylamine hydrochloride was performed in triplicate.

[0021] The method further comprises the step of:

b) forming a fibre web by dewatering a slurry comprising the modified

cellulose fibres.

[0022] To avoid premature fibrillation, the pH of the slurry of step b) is preferably below 9, such as 8 or lower, normally 4-8.

[0023] The fibre web preferably comprises more than 50 %, such as more than 70 %, such as more than 90 % modified fibres based on the total dry weight of the fibre web.

[0024] To the slurry, various additives may be added that forms part of the sheets to introduce functionalities to the sheet. Such additive can be graphite or graphene to produce a conductive sheet (see Example 8 below). The additive can also be cationic polymers that make the sheet antimicrobial, wherein examples of such cationic polymers are cationic polyvinylamine (PVAm) and cationic chitosan. It is possible to add more than one type of additive to introduce multiple functionalities. Instead of addition to the slurry, the additive(s) can also be added together with the base in step c).

[0025] Step b) preferably comprises dewatering the slurry on a forming wire of a paper machine. It may further comprise dewatering the fibre web in a press section of a paper machine and/or drying the fibre web in a drying section of a paper machine. In a particularly preferred embodiment, step b) comprises all three steps, i.e. dewatering the slurry on a forming wire of a paper machine to form the fibre web, dewatering the fibre web in a press section of the paper machine and drying the fibre web from the press section in a drying section of the paper machine.

[0026] The method further comprises the step of:

c) adding a base to the fibre web so as to obtain the sheet comprising

fibrillated cellulose. [0027] The base may for example be an hydroxide of an alkali metal or an alkaline earth metal, such as sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide Mg(0H) ₂ or calcium hydroxide Ca(0H) ₂ . The base may for example also be ammonia or ammonium hydroxide. The base may for example also be salts of carbonates, carbanions, amides and hydrides, such as sodium carbonate

(NaC0 ₃ ), sodium amide (NaNH ₂ ), sodium borohydride (NaBH ₄ ) or lithium borohydride (LiBH ₄ ). The type of base can affect the final properties of the sheet. NaBH ₄ , which reduces aldehydes to alcohols, may be a particularly suitable base as it has been shown to result in higher tensile strength in the final product than NaOH (see Example 7b).

[0028] Step c) maybe carried out online, i.e. in a paper machine, or offline, i.e. in an arrangement that is separate from the paper machine. In the online case, step c) may be carried out in the drying section, i.e. before the drying is completed, or downstream the drying section, e.g. between the drying section and a reel section. In the former case, the drying section can be used to remove water that is added to the fibre web together with the base (addition of aqueous base is further discussed below). In the latter case, such water can be removed by extra drying equipment arranged downstream the point of the addition according to step c).

[0029] The moisture content of the web just before the addition of the base according to step c) may for example be 5-30 wt.%, such as 5-20 wt.%, such as 5-15 wt.%. Accordingly, the web maybe dried in step b) to a moisture content of 5-30 wt.%, such as 5-20 wt.%, such as 5-15 wt.%.

[0030] In one embodiment, the dried fibre web may be rewetted with water prior to conducting step c). Rewetting is suitably performed by one or several spraying device(s) or by means of one or several roller(s) or by means of one or several tank(s) in where the web is submerged or by a combination of spraying device(s) and/or roller(s) and/or tank(s). Drying of the fibre web to a moisture content below 10 wt.% in step b) is particularly advantageous when performing step c) offline. In such case the web can be produced and dried in one arrangement (typically a paper machine), and thereafter transported to another arrangement where step c) is performed to obtain the sheet with fibrillated fibres. Accordingly, in one embodiment, the rewetting and step c) is carried out offline. [0031] Alternatively, the moisture content of the web just before the addition according to step c) may for example be 40-60 wt.% since such a moisture content would facilitate the distribution of the base throughout the web.

[0032] In step c), the base may for example be added as an aqueous composition comprising alkali or another base. Such a composition may for example have a pH of 9.5-14. In an embodiment, the pH is 9.5-12, such as 9.5-11. In another embodiment, the pH is 10-14, preferably 10-12. In yet another embodiment, the pH is 11-14, such as 12-14. A pH above 12 typically requires washing and/or neutralization. It is preferred to have a pH of below 12 since a pH at 12 or above may fibrillate the web to such an extent that mechanical properties are negatively affected. On the other hand, it may be beneficial to have a high pH (e.g. above 12 or higher) to increase transparency. The composition preferably comprises a polymer, such as starch, carboxymethylated cellulose (CMC) or polyvinyl alcohol (PVOH). In addition to the polymer, the composition may comprise a rheology modifier.

[0033] In one embodiment, step c) comprises spraying the composition onto the fibre web.

[0034] In an alternative or complementary embodiment, a size press is used for the addition of the composition. The viscosity the composition that is added in a size press is typically 10-1000 mPas, preferably 10-300 mPas, when measured as dynamic viscosity with a Brookfield rotational viscometer using spindle no.4 at 100 rpm and 25 °C according to the Brookfield instruction sheet.

[0035] According to another embodiment, a curtain coater or a direct rod coater is used for the addition of the composition. The viscosity of the composition that is added in a curtain coater is typically 100-800 mPas when measured as dynamic viscosity with a Brookfield rotational viscometer using spindle no.4 at 100 rpm and 25 °C according to the Brookfield instruction sheet.

[0036] According to yet another embodiment, a blade coater is used for the addition of the composition. The viscosity of the composition that is added in a blade coater is typically 400-1500 mPas when measured as dynamic viscosity with a Brookfield rotational viscometer using spindle no.4 at 100 rpm and 25 °C according to the

Brookfield instruction sheet. [0037] In an embodiment, the composition comprises a crosslinking agent, such as a zirconium-based cross-linker. The zirconium-based cross-linker may for example by a zirconium carbonate, such as ammonium zirconium carbonate or potassium zirconium carbonate. A specific example of a zirconium-based cross-linker is Zirlink available from Brenntag Nordic AB (Sweden). The inclusion of the zirconium-based cross-linker is of particular interest when the polymer of the composition comprises hydroxyl and/ or carboxyl groups.

[0038] The composition may comprise CaC0 ₃ pigment. In such case, the result of adding the composition is not only that fibrillation is triggered, but also to that a pigment coating is formed on the web. Such a pigment composition may for example have a pH of 9-12, such as 10-12, such as 10-11. The pigment composition typically comprises a polymeric binder, such as starch or latex. The pigment composition may be added by any one of the coating techniques mentioned above (even if spraying is less preferred in case of a pigment composition). Appropriate viscosities for the respective method are also mentioned above. If a size press is used, the viscosity of the pigment composition is preferably 100-300 mPas when measured as dynamic viscosity with a Brookfield rotational viscometer using spindle no.4 at 100 rpm and 25 °C according to the Brookfield instruction sheet.

[0039] The method may further comprise the step of drying the sheet formed in step c). Thereby, a film having one or more of the following properties maybe obtained: a density of the sheet according to ISO: 2011 534 that is at least 0.8 g/cm ³ , such as at least 1.0 g/cm ³ , such as at least 1.2 g/cm ³ , wherein an upper limit maybe 1.6, 1.8 or 2.0 g/cm ³ ; a tensile strength of 90-170 MPa (measured on samples that were 5 mm wide and 100 pm thick at a straining rate of 3 mm/min using an Instron 5944, equipped with a 500 N load cell, in a controlled climate of 23 °C and 50% RH); a total transmittance of at least 70%, such as 70-90% measured at a wavelength of 550 nm with a Shimadzu UV- 2550UV-VIS spectrophotometer equipped with its integrating sphere accessory; and an oxygen permeability (OP) of less than 15 cm ³ mm m ^-2 d ^-1 kPa ^-1 at 23°C and 50% RH, such as less than 10 cm ³ mm m ^-2 d ^-1 kPa ^-1 at 23°C and 50% RH, such as less than 5 cm ³ mm m ^-2 d ^-1 kPa ^-1 at 23°C and 50% RH, such as 0.05-5 cm ³ mm m ^-2 d ^-1 kPa ^-1 at 23 °C and 50% RH, such as 0.5-5 cm ³ mm m ^-2 d ^-1 kPa ^-1 at 23 °C and 50% RH (as measured on samples with 100 pm thickness according to ASTM D3985 and F1927 standards). [0040] In an embodiment, the sheet comprising fibrillated cellulose is a layer of a multi-layered material. In such case, step b) may comprise forming the web on a substrate comprising cellulose fibres. For such a formation, the slurry comprising the modified cellulose fibres may be sprayed onto a forming web comprising cellulose fibres. Alternatively, the slurry comprising the modified cellulose fibres may be added to a forming web comprising cellulose fibres by means of a headbox, such as a stratified headbox that is also used for the forming web. Yet another alternative is to form the fibre web from the slurry comprising the modified cellulose fibres on a first wire, while a second wire is used to form a second fibre web, which second fibre web is subsequently adhered to the fibre web from the slurry comprising the modified cellulose fibres, preferably by couching.

[0041] In an embodiment, the method further comprises the step:

d) adding an acid to the sheet comprising fibrillated cellulose to neutralize chargeable moieties of the fibrillated cellulose.

[0042] In addition to neutralization of charges, the formation of hemiacetals are promoted upon addition of acid, whereas hemiacetals are broken into alcohols and aldehydes at high pH.

[0043] The acid may be for example be a strong acid such as HC1, H ₂ SO4, HNO _3, HI, HC1O4 or HC1O3. The acid may for example also be a weak acid such as H _{2 3} , HCO ₂ H, H ₃ PO ₄ , HNO ₂ , HF or citric acid. If a weak acid is used a longer exposure time is needed compared with when a strong acid is used. An exposure time of below 5 minutes, such as below 2 minutes, is suitable for strong acids. An effect of neutralization of charges is decreased moisture-induced swelling of the sheet and thus maintained barrier properties at increased relative humidity (see example 7C).

[0044] Step d) may be carried out online, i.e. in a paper machine, or offline, i.e. in an arrangement that is separate from the paper machine. In the online case, step d) may be carried out in the drying section, i.e. before the drying is completed, or downstream the drying section, e.g. between the drying section and a reel section. In both the online and the offline case, step d) is carried out after step c). It is possible to perform both step c) and d) online or offline as well as carry out step c) online and step d) offline. In the latter case the sheet comprising fibrillated cellulose produced in step c) is preferably rewetted prior to carrying out step d). [0045] As a second aspect of the present disclosure, there is provided a method of producing a fibre web, comprising the steps of:

I. providing chemically modified cellulose fibres in which a chargeable

moiety has been introduced and the C ₂ -C ₃ bond has been broken in at least part of the D-glucose units, wherein the charge density measured according to SCAN-CM 65:02 is 150-1500 meq/g;

II. applying a slurry comprising the modified fibres to a forming wire of a paper machine;

III. dewatering the slurry on the forming wire of the paper machine to form a fibre web;

IV. further dewatering the fibre web in a press section of the paper machine; and

V. drying the fibre web from the press section in a drying section of the paper machine to a density of o.8-1.8 g/cm ³ , such as 1.0-1.6 g/cm ³ .

[0046] Paper machine is referring to a full-scale paper machine. The width of the wire in the paper machine is suitably 5-8 m, and the width of the press section as well as the width of the drying section are adapted accordingly. The machine speed in the wire section is at least 100 m/min.

[0047] What is described above with respect to the first aspect and in particular steps a) and b) thereof applies to the second aspect mutatis mutandis.

ITEMIZED LISTING OF EMBODIMENTS

This is an itemized listing of embodiments of the present disclosure:

1. A method of producing a sheet comprising fibrillated cellulose, comprising the steps of:

a) chemically modifying cellulose fibres to introduce a chargeable moiety and break the C ₂ -C ₃ bond in at least part of the D-glucose units so as to obtain modified cellulose fibres having a charge density measured according to SCAN-CM 65:02 of 150-1500 meq/g;

b) forming a fibre web by dewatering a slurry comprising the modified

cellulose fibres; and c) adding a base to the fibre web so as to obtain the sheet comprising fibrillated cellulose.

2. The method according to item 1, wherein a dialdehyde is formed when the C ₂ -C ₃ bond is broken.

3. The method according to item 2, wherein step a) comprises periodate oxidation to break the C ₂ -C ₃ bond.

4. The method according to any one of the preceding items, wherein the chargeable moiety is introduced in step a) by oxidation, carboxymethylation, phosphorylation or sulfonation.

5. The method according to item 4, wherein the oxidation is TEMPO oxidation or chlorite oxidation.

6. The method according to any of the preceding items, wherein the introduction of the chargeable moiety is followed by periodate oxidation to break the C ₂ -C ₃ bond in step a).

7. The method according to item 5, wherein step a) comprises chlorite oxidation to introduce the chargeable moiety subsequent to the periodate oxidation.

8. The method according to any one of the preceding items, wherein the carbonyl content of the modified cellulose fibres is 1.0-7.0 mmol/g, such as 1.5-6.0 mmol/g.

9. The method according to any one of the preceding items, wherein the modified cellulose fibres have a charge density measured according to SCAN-CM 65:02 of 200- 900 meq/g, such as 250-700 meq/g.

10. The method according to any one of the preceding items, wherein step c) comprises adding an aqueous composition comprising the base onto the fibre web, e.g. by spraying.

11. The method according to item 10, wherein the pH of the aqueous composition is 9.5-14, preferably 9.5-12, such as 9.5-11, such as 10-14, preferably 10-12, such as 11-14, such as 12-14.

12. The method according to item 10 or 11, wherein the aqueous composition further comprises a polymer, such as starch, carboxymethylated cellulose (CMC) or polyvinyl alcohol (PVOH). 13. The method according to any one of items 10-12, wherein:

a size press is used for the addition of the aqueous composition and the viscosity of the aqueous composition is 10-1000 mPas, preferably 10-300 mPas;

a curtain coater or a direct rod coater is used for the addition of the aqueous

composition and the viscosity of the aqueous composition is 100-800 mPas; or a blade coater is used for the addition of the aqueous composition and the viscosity of the aqueous composition is 400-1500 mPas,

and wherein the viscosity is measured as dynamic viscosity with a Brookfield rotational viscometer using spindle no.4 at 100 rpm and 25 °C.

14. Method according to any one of the preceding items, wherein the pH of the slurry of step b) is below 9, such as 8 or lower.

15. Method according to any one of the preceding items, wherein the fibre web in step b) is dried to a moisture content of below 30 wt.%, such as below 20 wt.%, such as below 15 wt.%, after dewatering and prior to conducting step c).

EXAMPLES

Example la

[0048] Alkaline TEMPO-mediated oxidation of fibres

[0049] TEMPO oxidation of never-dried bleached softwood kraft pulp (ND BSKP) from BillerudKorsnas AB (Gruvön pulp mill, Grams, Sweden) was performed in alkaline media in order to predominantly introduce carboxyl groups to the C6 position on cellulose. Amounts of 0.1 mmol 2,2,6,6-tetramethyl-i-piperidineyloxy (TEMPO), 1 mmol sodium bromide (NaBr) and 9.7 mmol sodium hypochlorite (NaC1O) per gram of dry fibre were added to a 12 g/L fibre suspension and kept to react for 1.5 h under gentle stirring at room temperature. The reaction pH was maintained at 10.5 by periodically dropwise addition of 0.5 M NaOH to the suspension. The reaction was terminated by filtering off the chemicals followed by thorough washing with deionized water and resulted in fibres with a total charge of 1.3 mmol/g, corresponding to 1300 meq/g. The TEMPO oxidation is further illustrated in Fig. 1, step (i).

[0050] Periodate oxidation of TEMPO-oxidized fibres in Example la

[0051] To the TEMPO-oxidized pulp, 5.4 g sodium periodate (NaIO ₄ ) was added per gram of dry fibre in a 12 g/L fibre suspension under gentle stirring further containing 6.3 vol % 2-propanol as radical scavenger to prevent side reactions. The fibres were oxidized for 45 minutes at 70 °C in the dark to further limit side reactions. The reaction was terminated by filtering off the chemicals followed by thorough washing with deionized water until the conductivity of the filtrate was <5 meq. The total charge of the resulting material was measured by titration and found to be 450 meq/g and the carbonyl content 3.1 mmol/g. The periodate oxidation is further illustrated in Fig. 1, step (ii).

Example lb

[0052] Periodate oxidation to total charge of 1000 meq/g from TEMPO-oxidized fibres in Example la

[0053] To the TEMPO-oxidized pulp in Example la, 2.7 g sodium periodate (NaIO ₄ ) was added per gram of dry fibre in a 12 g/L fibre suspension under gentle stirring further containing 6.3 vol % 2-propanol as radical scavenger to prevent side reactions. The fibres were oxidized for 45 minutes at 70 °C in the dark to further limit side reactions. The reaction was terminated by filtering off the chemicals followed by thorough washing with deionized water until the conductivity of the filtrate was <5 meq. The total charge of the resulting material was measured by titration and found to be 1000 meq/g and the carbonyl content 1 mmol/g.

Example IC

[0054] Periodate oxidation at room temperature of TEMPO-oxidized fibres in Example la to 700 meq/g

[0055] To the TEMPO-oxidized pulp in Example la, 3.15 g sodium periodate (NaIO ₄ ) was added per gram of dry fibre in a 12 g/L fibre suspension under gentle stirring further containing 6.3 vol % 2-propanol as radical scavenger to prevent side reactions. The fibres were oxidized for 24 h in the dark to further limit side reactions. The reaction was terminated by filtering off the chemicals followed by thorough washing with deionized water until the conductivity of the filtrate was <5 meq. The total charge of the resulting material was measured by titration and found to be 700 meq/g and the carbonyl content 7 mmol/g.

Example 1d

[0056] Periodate oxidation at room temperature of TEMPO-oxidized fibres in Example la to 880 meq/g [0057] TEMPO-oxidation and periodate oxidation was performed at room temperature according to Example 1C resulting in a total charge of the final material that was measured by titration and found to be 880 meq/g and the carbonyl content 2.6 mmol/g.

Example le

[0058] Neutral TEMPO-mediated oxidation of fibres

[0059] TEMPO oxidation of ND BSKP was conducted in phosphate buffer (pH 6.8). Amounts of TEMPO (1 mmol), NaCIO (10 mmol) and NaC102 (100 mmol) were added and kept to react for 2.5h under gentle stirring at 60 °C. The reaction was terminated by filtering off the chemicals followed by thorough washing with deionized water and resulted in fibres with a total charge of 650 meq/g.

[0060] Periodate oxidation of the TEMPO-oxidized fibres in Example le

[0061] To the TEMPO-oxidized pulp in Example le, 5.4 g sodium periodate (NaIO ₄ ) was added per gram of dry fibre in a 12 g/L fibre suspension under gentle stirring further containing 6.3 vol % 2-propanol as radical scavenger to prevent side reactions. The fibres were oxidized for 45 minutes at 60 °C in the dark to further limit side reactions. The reaction was terminated by filtering off the chemicals followed by thorough washing with deionized water until the conductivity of the filtrate was <5 meq. The total charge of the resulting material was measured by titration and found to be 450 meq/g and the carbonyl content 2.5 mmol/g.

Example if

[0062] A neutral (pH 6.8) TEMPO-mediated oxidation of the ND BSKP resulted in a pulp material with approximately 450 meq/g charge. The TEMPO-oxidized material was then subjected to periodate oxidation according to Example la. The total charge of the resulting material was measured by titration and found to be 370 meq/g.

Example lg

[0063] A neutral (pH 6.8) TEMPO oxidation of the ND BSKP resulted in a pulp material with approximately 380 meq/g charge. The TEMPO-oxidized material was then subjected to periodate oxidation according to Example la. The total charge of the resulting material was measured by titration and found to be 180 meq/g with carbonyl content of 3.8 mmol/g. Example 2

[0064] Periodate oxidation of carboxymethylated fibres

[0065] Carboxymethylated pulp (Mare, Austria) from fully bleached softwood fibres with a charge of 500 mmol/g was subjected to periodate oxidation. To a pulp suspension (12 g/L) further containing 6.3 vol% 2-propanol, 4.05 g NaIO ₄ was added per gram of dry fibre under gentle stirring (250 rpm). The fibres were oxidized for 45 minutes at 60 °C in the dark. The reaction was terminated by filtering off the chemicals followed by thorough washing with deionized water until the conductivity of the filtrate was <5 meq. The total charge of the resulting material was measured by titration and found to be 380 meq/g with carbonyl content of 4.2 mmol/g.

Example 3

[0066] Periodate oxidation followed by chlorite oxidation

[0067] A suspension of ND BSKP (18 g/L) with 6.3 vol% 2-propanol was prepared and brought up to 60 °C under stirring (500 rpm). Once the suspension had reached 60 °C, NaIO ₄ was added at a ratio of 3.038 g NaIO ₄ per 1 g of dry fibre. The reaction was conducted under in the dark for 45 minutes and the fibres were thereafter washed with deionized water until the conductivity of the filtrate was <5 meq. The carbonyl content of the obtained dialdehyde cellulose (DAC) was measured by titration and found to be carbonyl content 4.5 mmol/g.

[0068] Chlorite Oxidation

[0069] The periodate oxidized fibres (i.e. DAC fibres) were subjected to partial chlorite oxidation. To a suspension of DAC fibres (9.3 g/L), sodium chlorite (NaC1O ₂ ,

2.5 mmol per 1 mmol of aldehyde) and hydrogen peroxide (H ₂ O ₂ , 2.5 mmol per 1 mmol of aldehyde) was added under gentle stirring at room temperature. The pH was brought down to 5 under gentle stirring (250 rpm) and the reaction was conducted under these conditions for 45 minutes the fibres were then washed with deionized water until conductivity of the filtrate was <5 ueq The total charge of the resulting material was measured by titration and found to be 750 meq/g with carbonyl content of 3.1 mmol/g.

Example 4

[0070] Periodate oxidation followed by phosphorylation [0071] ND BSKP fibres (5 g/L) were refined in a PFI mill for 4000 rev, and thereafter fractionated by continuous washing with approximately 10 L of deionized water in a Bauer McNett with a 50 mesh metallic wire to remove the fines liberated during the refining and the concentration was set to 10 g/L. Phosphorylation of the fibres was carried out by impregnation under continuous stirring with (NH ₄ ) ₂ HPO ₄ in the presence of urea in the following molar ratios: 1:2.5:10 (anhydroglucose units of the fibers: (NH ₄ ) ₂ HPO ₄ : Urea) followed by filtration to obtain a 100 g/L fibre dispersion. The fibres were then dried in an oven at 50 °C, followed by curing at 150 °C for 10 min, and washing with 2 L of boiling and 2 L of cold deionized water to remove loosely attached chemicals. Excess amounts of urea are usually used in phosphorylation to prevent the degradation of cellulose due to the release of phosphoric acid during curing at elevated temperatures. The total charge of the resulting material was measured by titration and found to be 730 meq/g.

[0072] The phosphorylated fibres were subjected to periodate oxidation under the following conditions. A pulp suspension (12 g/L) with 6.3 vol% 2-propanol was prepared and brought up to 60 °C under gentle stirring (250 rpm). Once the suspension reached 60 °C, NaIO ₄ was added at a ratio of 5.4 g NaIO ₄ per 1 g of dry fibre. The reaction was conducted in the dark for 45 minutes and then the fibres were washed with deionized water until the conductivity of the filtrate was <5 meq. The total charge of the resulting material was measured by titration and found to be 200 meq/g with carbonyl content of 5 mmol/ g

Example 5

[0073] Periodate oxidation followed by sulfonation

[0074] A suspension of ND BSKP (18 g/L) with 6.3 vol% 2-propanol was prepared and brought up to 60 °C under stirring (500 rpm). Once the suspension had reached 60 °C, NaIO ₄ was added at a ratio of 3.038 g NaIO ₄ per 1 g of dry fibre. The reaction was conducted under in the dark for 45 minutes and the fibres were thereafter washed with deionized water until the conductivity of the filtrate was <5 meq. The obtained

dialdehyde cellulose (DAC) was assumed to have a carbonyl content of 4.5 mmol/g.

[0075] Sulfonation

[0076] The periodate oxidized fibres (i.e. DAC fibres) were subjected to partial sulfonation. To a suspension of DAC (20 g/L), 2.2 mmol Na ₂ S ₂ O ₅ /mmol aldehyde was added under gentle stirring at room temperature and left stirring for 4 hours. The total charge of the resulting material was measured by titration and found to be 1190 meq/g and the carbonyl content 5.1 mmol/g.

Example 6

[0077] Sheet preparation from the fibres of Example la with grammage 100 g/ m ²

[0078] Paper sheets with a target grammage of 100 g/m ² were prepared using a vacuum filtration set up equipped with a standard Rapid Kothen sheet former (Paper Testing Instruments, Austria) wire. Pulp fibres from Example la were suspended and protonated at pH 2 for 10 minutes in order to ensure de-swelling and consolidation of the individual fibres and fibrils prior to sheet forming. Once the paper was formed, it was either directly peeled off the forming wire (Example 6a) or dried (Example 6b) prior to sheet preparation.

Example 6a

[0079] Sheet Preparation from moist paper of Example 6

[0080] Nanofibrillation was achieved via immersion of the moist paper in a NaOH solution at pH 10 (approximately 1-2 minutes), and hence a nanopaper was obtained and dried.

Example 6b

[0081] Sheet Preparation from dry paper of Example 6

[0082] The moist paper was dried at 93 °C under vacuum (reduced pressure of 95 kPa) for 12 minutes. The dried sheet was thereafter rapidly immersed in water (de- ionized) to moisten the surface and thereafter immersed in a NaOH solution at pH 10 (approximately 1-2 minutes), and hence a nanopaper was obtained and dried.

Example 7

[0083] Sheet preparation from the fibres of Example id with grammage 80 g/m ²

[0084] Paper sheets with a target grammage of 80 g/m ² were prepared from pulp fibres from Example id using a vacuum filtration set up equipped with a standard Rapid Kothen sheet former (Paper Testing Instruments, Austria) wire.

Example 7a

[0085] Sheet preparation of paper from Example 7 [0086] Nanofibrillation was achieved via immersion of the moist paper from

Example 7 in a NaOH solution at pH 12 (5 minutes), and hence a nanopaper was obtained, that was rinsed with de-ionized water and dried.

Example 7b

[0087] Sheet Preparation from dry paper with NaBH ₄ as base

[0088] Nanofibrillation was achieved via immersion of the moist paper from

Example 7 in NaOH (pH 9) for 1 minute followed by exposure to NaBH ₄ (1 g/g fibre) for 5 minutes and thereafter rinsed with de-ionized water and dried.

Example 7C

[0089] Neutrally charged Sheet Preparation

[0090] Nanofibrillation was achieved via immersion of the moist paper from

Example 7 in a NaOH solution at pH 12 (5 minutes), and hence a nanopaper was obtained, that was rinsed with de-ionized water followed by immersion in HC1 (pH 2) for 5 minutes to neutralize the charges on the charged moieties, and thereafter rinsed again with de-ionized water and dried.

Example 8

[0091] Sheet Preparation with graphite inclusion

[0092] Fibrillated paper sheets with a target grammage of 100 g/m ² were also prepared according to Example 6, with the addition of graphite (approximately 20 pm diameter) that was added to the fibre suspension at a dry weight-ratio of 1:2

(fibers: graphite) prior to production of the sheets.

Comparative Example 1

[0093] Periodate oxidation followed by TEMPO-oxidation

[0094] The procedure described in Example la was conducted in reversed order, i.e. periodate oxidation followed by alkaline TEMPO-mediated oxidation. During the TEMPO-oxidation the fibres swelled and fibrillated pre-maturely due to the alkaline nature of the TEMPO oxidation.

Comparative Example 2

[0095] Periodate oxidation, sheet formation and addition of alkali [0096] Periodate oxidation was performed on ND BSKP without any prior TEMPO oxidation. The periodate oxidation was performed as described in Example la.

Thereafter, sheets were formed and alkali added according to Example 5. The sheet structure was disintegrated, but the fibres did not fibrillate.

Comparative Example 3

[0097] Chlorite oxidation to high charge followed by periodate oxidation

[0098] To ND BSKP, periodate oxidation according to the procedure of Example 3 was conducted followed by chlorite oxidation using NaC102 (10 mmol) and H2O2 (10 mmol) at pH 5 for 3h so that the charge of the modified fibres became 2000 mmol/g. Upon stirring the fibres fibrillated and could, thus, not be formed into a sheet on a wire.

Characterization methods

[0099] Pulp Characterization

[00100] The total charge of the pulp was determined via conductiometric titration using a Metrohm 702SM Titrino titrator according to the SCAN-CM 65:02 standard.

The aldehyde content (assumed to be equivalent to the carbonyl content) was determined by stoichiometric reaction with hydroxylamine, which releases a

stoichiometric amount of protons. The amount of protons released was then determined by titration with NaOH. Each titration was performed in triplicate.

[00101] Fibrillation upon addition of base?

[00102] To test if the fibres fibrillate upon addition of base, the pulp was suspended in a vial under neutral pH and the pH was then adjusted to approximately 12 by the addition of NaOH. If the suspension turned completely clear and transparent (visual inspection), the fibres were considered to be fibrillated.

[00103] Measuring the level of fibrillation

[00104] In order to quantify the amount of nanofibrillation taking place in different samples, a simple protocol was developed. The test was based on the assumption that truly liberated CNFs are colloidally stable and hence do not sediment when centrifuged in a dispersion. A 200 ml fibre suspension with a consistency of 1 g/L was brought to pH 12, divided into five conical Falcon tubes and centrifuged at 4120 RCF for 1 h. The supernatant was decanted from the tubes and the sediment was filtered using a filter membrane, 0.65 pm DVPP membrane (Merck Millipore, Burlington, MA) to be weighed after they are oven dried. Finally, the degree of fibrillation was calculated as the mass fraction found in the supernatant (i.e. fraction not found in the sediment).

[00105] Mechanical Testing

[00106] Tensile tests were performed on samples that were 5 mm wide and 100 pm thick using an Instron 5944, equipped with a 500 N load cell, in a controlled climate of 23 °C and 50% RH. Samples were clamped with a free span of 30 mm and strained at a rate of 3 mm/min. The strain was determined by measuring the grip displacement and the Young’s modulus was calculated as the slope of the initial linear part of the stress vs. strain plot, in this case in the 0.5 - 1% strain interval. A total of ten test pieces were tested per sample.

[00107] Oxygen Permeability

[00108] The oxygen permeability was measured on 100 mm thick 5 cm ² samples using a MOCON OX-TRAN 2/21 according to the ASTM D3985 and ASTM F1927 standards. The oxygen permeability measurements were performed at 23 °C and 50% RH or 80% RH, using the same relative humidity on both sides of the sample. The measurements were performed in duplicates.

[00109] Transmittance

[00110] The total transmittance (T) of the nanopapers were measured using a

Shimadzu UV-2550 UV-vis spectrophotometer equipped with an integrating sphere accessory. Measurements were taken at three random points on each sample and measurements were performed in triplicates.

Results

[00111] In Table 1 charge densities of the modified cellulose fibres as well as if the fibres can be fibrillated by addition of alkali is presented. As can be seen, fibres that can be turned into a web on a wire and thereafter fibrillated are obtained only when the chemical modification include the introduction of a chargeable moiety as well as a breakage of C2-C3 bonds.

[00112] When C2-C3 bonds are broken by periodate oxidation, dialdehydes are formed. At low pH values, hemiacetals formed by the dialdehydes hold the fibre wall together despite the cumulative softening caused by the charge introduction, thus preventing the fibre wall from falling apart and thereby slipping through the formation wire. Once the web formation is completed, the sample can be exposed to high pH conditions that will synergistically hydrolyse the hemiacetal linkages and cause osmotic swelling, hence liberating the fibrils by“exploding” the fibre wall into its constituents. The pH-dependence of fibrillation of fibres modified according to the present disclosure is further illustrated in Fig. 2.

[00113] The mechanism behind the highly pH responsive fibrillation behaviour of the modified fibres is thus suggested to be primarily controlled by two parameters: the amount of charges that facilitate swelling and an opening of the fibrillar structure in the fibre wall, and the amount of hemiacetal bonds that assist in keeping the network together at higher degree of modification.

[00114] “Charged fibres” that have intact C2-C3 bonds typically require high-energy mechanical procedures, such as microfluidization or homogenization, to fibrillate due to the still existing structural integrity of the fibre wall, unless the charge density is so high that the fibres fibrillate prematurely already by the impact of the agitation during chemical modification or the subsequent sheet forming process (illustrated by comparative example 3).

Table 1. Charge measurements and fibrillation test.

[00115] In Table 2 dewatering times for fibres modified according to the present disclosure (Example la) as well as reference values reported elsewhere for unmodified or chemically modified CNF are presented. In the latter case, the chemical modification was conducted prior to fibrillation (ref. 1-3). Further, a nanopaper was formed from the fibres of the present disclosure according to the procedure of Example 6a (without intermediate drying) and Example 6b (with intermediate drying). The mechanical, barrier and optical properties of this paper was compared to those of the nanopapers prepared from CNF (see ref. 1-3).

[00116] The nanopapers produced according to Examples 6a and 6b exhibited comparable mechanical and barrier properties as well as transparency to those of nanopapers produced from the different types of CNF reported previously. These results demonstrate that nanopapers can be produced much faster compared with conventional techniques without having to sacrifice performance.

[00117] Moreover, since the fibres are dewatered prior to nanofibrillation, a lower amount of water is present during transport compared with CNF suspensions used for nanopaper production. In fact, it is even so that the pH induced nanofibrillation can be performed on dried modified fibre sheets according to the invention (confirmed by SEM images, data not shown), which is beneficial since no excess water needs to be transported together with the fibres and fibrillation can be performed off-site.

[00118] The resistance of the fibrillated sheets with graphite inclusion produced in Example 8 was 50 W. In contrast, the resistance of fibrillated sheets without graphite was not measurable and hence it is concluded that such a sheet is an insulator.

Table 2. Measurements of dewatering time of modified fibres (Example la), and mechanical properties as well as OTR and transmittance of sheet comprising cellulose fibrils. As well as comparison with previous reported values (Ref. 1-3).

a Modified fibres according to Example la; ^b Measured on a sheet prepared from the modified fibres of Example la according to Example 6 prior to fibrillation; ^c Measured on a sheet prepared from the modified fibres of Example la and fibrillated directly when moist according to Example 6a; ^d Measured on a sheet prepared from the modified fibres of Example la and pre-dried according to Example 6b prior to fibrillation by immersion in NaOH.

¹ Osterberg, M. et al. A Fast Method to Produce Strong NFC Films as a Platform for Barrier and Functional Materials. ACS Appl. Mater. Interfaces 5, 4640-4647 (2013).

² Fujisawa, S., Okita, Y., Fukuzumi, H., Saito, T. & Isogai, A. Preparation and characterization of TEMPO-oxidized cellulose nanofibril films with free carboxyl groups. Carbohydr. Polym. 84.

3 Aulin, C., Gallstedt, M. & Lindstrom, T. Oxygen and oil barrier properties of microfibrillated cellulose films and coatings. Cellulose 17, 559-574 (2010).

[00119] In table 3 the sheets of Examples 7a, 7b and 7c are presented. The sheets according to Example 7a and 7c were fibrillated with NaOH (pH 12), whereas the sheets produced according to Examples 6a and 6b were fibrillated with NaOH (pH 10), wherein pH 12 results in a lower strain to failure and tensile strength compared with pH 10. [00120] The sheet prepared with NaBH ₄ as the base according to Example 7b had a tensile strength that was about 20% higher than that of the sheet prepared with NaOH according to Example 7a.

[00121] The sheet prepared with NaOH as base and thereafter charge-neutralized with HC1 had a maintained OP even when increasing the RH to 80 %.

¹ Modified fibres according to Example id and fibrillated with NaOH; ¹¹ Modified fibres according to Example id and fibrillated with NaBH ₄ ; ¹¹¹ Modified fibres according to Example id and fibrillated with NaOH followed by neutralization with HC1.

N.M.: Not measured.