Method for improving the water tolerance of bio-based CNF-films

Abstract

The present invention relates to a continuous roll-to-roll process for improving the water tolerance of bio-based polymers, in particular cellulose nanofibrils (CNF) films. Furthermore, the invention provides a method, which combines surface modification/functionalization for improving water stability and wet strength, UV/Ozone treatment, corona treatment or plasma activation for purifying and activating the surface and thus increasing the reaction efficiency, and further hydrophobization of the surface of CNF film.

Claims

1. A method of improving water tolerance of a cellulose nanofibril (CNF) film having two opposite surfaces, wherein the method comprises: protecting both surfaces of the CNF film from moisture and includes the steps of: a) preparing a CNF suspension and modifying the suspension by adding polymers containing charged, hydrophobic or polar functional groups into the suspension, b) applying and spreading the CNF suspension directly onto a surface of a plastic support material in order to prepare a CNF film, c) purifying and activating at least one surface of the CNF film with UV/Ozone treatment, corona treatment or plasma activation, and d) modifying the activated CNF film surface by plasma deposition, atomic layer deposition (ALD) or sol-gel method, or any combination thereof.

2. The method according to claim 1, wherein the method is continuous and utilizes roll-to-roll technology.

3. The method according to claim 1, wherein the CNF suspension contains a maximum of 2 wt-%, but preferably between 0.25 and 2 wt-% of unmodified nanofibrillated cellulose.

4. The method according to claim 1, further comprising modifying the CNF suspension by adding polymers containing functional groups having one or more O, S or N atoms or one or more double bonds.

5. The method according to claim 1 further comprising modifying the CNF suspension by adding polymers containing hydroxyl groups or carboxyl groups, preferably selected from polyvinyl alcohol, polyacrylic acids and polycarboxylic acids, and a catalytic amount of acidic salts, such as ammonium chloride, ammonium sulfate, aluminum chloride, magnesium chloride, magnesium nitrate, or alkali metal salts of phosphorous-containing acids.

6. The method according to claim 1, wherein the plastic support material is preferably selected from polyolefins, such as polyethylene or polypropylene.

7. The method according to claim 1, further comprising carrying out plasma deposition, wherein a plasma unit is installed in a coating line and the plasma unit uses power between 200 W and 800 W.

8. The method according to claim 7, wherein gases selected from nitrogen, helium and argon are used as carrier gases for deposition chemicals and for plasma in the plasma deposition.

9. The method according to claim 7, wherein a deposition chemical(s) is (are) atomized prior to plasma unit.

10. The method according to claim 7, wherein hexamethyldisiloxane (HMDSO) is used as a deposition chemical.

11. A structure consisting of a cellulose nanofibril (CNF) film manufactured according to a method of improving water tolerance of the CNF film, said CNF film having two opposite surfaces, wherein the CNF film has a thickness between 15 and 150 μm, and wherein the method of improving water tolerance of the CNF film comprises protecting both surfaces of the CNF film from moisture and includes the steps of: a) preparing a CNF suspension and modifying the suspension by adding polymers containing charged, hydrophobic or polar functional groups into the suspension, b) applying and spreading the CNF suspension directly onto a surface of a plastic support material in order to prepare a CNF film.

12. The structure according to claim 11, wherein the CNF film is present as a coating on at least one surface of a support preferably made of plastic material, more preferably selected from polyolefins, such as polyethylene and polypropylene or polyethylene terephthalate.

13. The structure according to claim 11, wherein the CNF film is detached from the support.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG. 1 is a simplified process chart disclosing an embodiment of the present invention.

[0022] FIG. 2 is a bar chart showing the effect of ALD coating on water vapour transmission rate of CNF films at tropical conditions (38° C., 90% relative humidity).

[0023] FIG. 3 is a table showing the oxygen transmission rates of CNF films as measured at different relative humidities (RH) at 23° C. (cc×20 μm/m.sup.2/day).

[0024] FIG. 4 is a chart showing water contact angles i.e. increase in surface hydrophobicity of HMDSO plasma-deposited CNF films after 30 seconds of droplet deposition.

[0025] FIG. 5 is a chart showing water vapour transmission rates i.e. increase of water vapour barrier properties of HMDSO plasma-deposited CNF films measured at 23° C., 100/50% relative humidity.

DETAILED DESCRIPTION OF EMBODIMENTS

[0026] The present invention relates to a process for producing CNF films of high quality and excellent technical properties in an industrial scale.

[0027] Particularly, the present invention relates to a process, which combines plurality of unit operations for improving the water tolerance of CNF films. Such unit operations include preparing a CNF suspension with modifying substances, applying and spreading the suspension on at least one surface of a support material to form a film, treating the film surface for example with UV/Ozone and further modifying the film surface by for example plasma deposition, atomic layer deposition or sol-gel method.

[0028] Herein, “cellulose nanofibrils, CNF” are considered as very thin (around 20 nm) fibrils having a longitude of several μm.

[0029] Preferably, such a nanofibrillated cellulose is used, which can be dispersed into water or another solvent wherein the CNF forms a gel-like transparent material, which can be used for producing biodegradable and environmentally safe, homogenous and dense films. CNFs of the present invention are particularly unmodified. Thus, the CNF is preferably selected from those types having a film forming ability.

[0030] According to one embodiment of the invention, the CNF suspension is applied on a support made of plastic material. The material is preferably selected from the group of polyolefins, such as polyethylene or polypropylene. The support is especially selected from materials of low porosity to prevent the filtration of the CNF suspension. The materials used herein are suitable for roll-to-roll type continuous processes.

[0031] Both the nanofibrillated cellulose and the support material may be chemically modified, prior to the formation of the CNF film, by adding polymers containing charged, hydrophobic or polar functional groups, preferably selected from functional groups containing one or more O, S or N atoms or one or more double bonds, most suitably selected from hydroxyl and carboxyl groups.

[0032] As far as water tolerance is concerned, the CNF films can be made stable in water by using a simple esterification reaction. Depending on the CNF grade, by adding small amount of polymers containing hydroxyl groups (e.g. polyvinyl alcohol) or carboxyl groups (e.g. polyacrylic acid) and catalytic amount of acid to CNF suspension, the films can be made stable in water yielding improved film wet strength, which is one object of the invention.

[0033] According to one embodiment the chemical modification of the CNF suspension is carried out by adding hydroxyl groups or carboxyl groups, preferably selected from polyvinyl alcohol, polyacrylic acids and polycarboxylic acids, and a catalytic amount of acidic salts, such as ammonium chloride, ammonium sulfate, aluminum chloride, magnesium chloride, magnesium nitrate, or alkali metal salts of phosphorous-containing acids.

[0034] According to another embodiment, prior to the surface functionalization the CNF film surface is purified and activated with UV/Ozone treatment in order to improve the reaction efficiency, for example by making the surface more receptive to OH-groups. This step also eases up the following process steps. Other suitable purification/activation methods are corona treatment and plasma activation with nitrogen, helium or argon.

[0035] According to another embodiment of the invention, films can be further surface hydrophobized by roll-to-roll plasma deposition or by some other suitable technique such as inorganic atomic layer deposition (ALD) with Al.sub.2O.sub.3, ZnO, or TiO.sub.2. In the case of plasma deposition, a plasma unit is preferably installed in a film coating line. In the unit, deposition precursor chemicals are atomized prior to plasma equipment (see e.g. FIG. 1). Vaporized (atomized) chemicals are then carried into the receptive surface of the CNF film where they react. Different gases, such as nitrogen, helium or argon, may be used as the carrier gas for deposition chemicals and for plasma.

[0036] One possible option is to use hydrophobic HMDSO (hexamethyldisiloxane) deposition. In an embodiment, line speeds of from 1 to 100 m/min were used, and the gas feed for precursor was between 0.5 L/min and 6 L/min.

[0037] With the concept of the present invention, which may involve simple silylation reaction, also other functionalities can be introduced on CNF film surface, for example amine groups by using other precursors such as acetonitrile, allyl alcohol or 2-hydroxyethyl acrylate.

[0038] Furthermore, the hydrophobicity of CNF films may also be increased by adding hydrophobic additives such as nanoclays (e.g. montmorillonite) or using chemical or physical cross-linking, or with surface treatment, such as grafting and extrusion coating or laminating with synthetic polymers such as polyolefins or using thin coatings such as ceramic or organically modified hybrid materials (sol-gels) or atomic layer deposited (ALD) barrier coatings.

[0039] According to one particularly preferred embodiment of the present invention, the method of improving water tolerance of bio based CNF (cellulose nanofibrils) films (having two opposite surfaces) protects both surfaces of the CNF film from moisture and includes the steps of: [0040] a) preparing a CNF suspension and modifying the suspension by adding polymers containing charged, hydrophobic or polar functional groups into the suspension, [0041] b) preparing a CNF film by applying and spreading the CNF suspension of step a) directly onto a surface of a plastic support material, [0042] c) purifying and activating at least one surface of the prepared CNF film of step b) with UV/Ozone treatment, corona treatment or plasma activation and [0043] d) modifying the activated CNF film surface by plasma deposition, atomic layer deposition (ALD) or sol-gel method, or any combination thereof.

[0044] According to a further embodiment, the method as described above is continuous and utilizes roll-to-roll technology.

[0045] The cellulose nanofibrils are preferably bio-based, i.e. of plant or algae origin, and the CNF suspension contains maximum of 2 wt-%, but preferably between 0.25 and 2 wt-% of such cellulose nanofibers (i.e. CNF) from the total suspension.

[0046] The thickness of the dry film of CNF applied onto the support is preferably between 15 and 150 μm. The thickness of the support is not an essential parameter. However, generally the thickness of the used support ranges between 20 and 2000 μm.

[0047] The film may be present as a coating on at least one surface of the support, which is preferably made of a plastic material as described above. According to a further embodiment, the film may be used as such, i.e. without the presence of the support.

[0048] A structure consisting of a CNF film manufactured by the method as hereinabove described is also in the scope of the present invention. In such structure, the CNF film is present as a coating on at least one surface of a support preferably made of plastic material, more preferably selected from polyethylene, polypropylene or polyethylene terephthalate. It is preferred that in the structure CNF film has a thickness between 15 and 150 μm as stated earlier. As a coating CNF has preferably a thickness between 0.5 and 5μm.

[0049] According to a further embodiment the structure consists of the film of CNF, detached from the support.

[0050] The CNF films of the present invention can be applied for example to membranes for water purification, as well as for application of high barrier packaging and printed intelligence including disposable solar cells, biosensors and diagnostics.

[0051] Next, the present invention is illustrated by the following non-limiting examples. It should be understood, however, that the embodiments given in the description above and in the examples are for illustrative purposes only, and that various changes and modifications are possible within the scope of the claims.

EXAMPLE 1

Surface Modification of CNF Films

Nanofibrillated Cellulose and CNF Film Manufacture

[0052] Never dried birch pulp was provided by UPM Kymmene and it was used as starting material. The pulp was washed into a sodium form, as described by Solala et al., 2011. Fluidization of the pulp was conducted using a microfluidizer (MicroFluidics Corporation, Westwood, USA). The pulp was passed through the fluidizer six (6) times with a final consistency of approximately 2 wt-% of CNF in water. The film production method is a variation of solvent casting films manufacture and it is based on precise control of adhesion, spreading, drying and pressing of the CNF on a plastic substrate. A defined amount of suspension, in a concentration not higher than 2% of solids is coated on a pre-treated plastic substrate. After evaporation of the excess of solvent by controlled drying, the remaining CNF film is carefully separated from the plastic substrate and calenderer with defined time, pressure and temperature. Finally the film is rolled and ready for further use.

CNF Film Surface Modification

[0053] Film surface modification was achieved by functionalization of the surface with either silyl or amine groups of the already assembled film surface. The modification protocol is a slight variation for the already known method to modify nanofibrils in bulk, as described e.g. by Johansson et al., 2011. Films of about 40 mg were submerged in dimethylacetamide (DMA, 99%—Sigma-Aldrich) in a weight ratio 1:10 in a reaction vessel under continue nitrogen (g) flow to evacuate any remaining oxygen. The film was kept in DMA under magnetic agitation until the temperature reached 80° C. Either silylation (Hexamethyldisilazan (HMDS), >99%—Sigma-Aldrich) or amination (3-Aminopropyl)-trimethoxysilan (APTES), 97%—Sigma-Aldrich)

X-Ray Photoelectron Spectroscopy (XPS)

[0054] Surface chemical analysis of the self-standing films was studied using X-Ray photoelectron spectroscopy (XPS) with a Kratos Analytical AXIS 165 electron spectrometer with monochromatic A1 Ka irradiation at 100K. Details on acquisition parameters are reported in Johansson et al. (Johansson et al., Microchimica Acta 2002). Low resolution survey spectra and high resolution carbon (C 1s) and oxygen (O 1s) were collected from the samples at least 3 locations. Analyzed area was less than 1 mm2 and only the outmost 10 nm of the film were reached by this technique without inducing any degradation on the sample. (Johansson et al., Surface Interface Analysis, 2001) As an in-situ reference, ash-free 100% cellulose filter paper was analyzed. (Johansson et al. Surface Interface Analysis, 2001) Silicon (Si 2p) and Nitrogen (N 1s) were recorded using survey resolution and extended acquisition times. (Johansson et al., Soft Matter 2011)

Solid State Nuclear Magnetic Resonance (.sup.13C-NMR and .sup.29Si-NMR)

[0055] .sup.13C CP/MAS NMR measurements were performed at room temperature with a Chemagnetics CMX 270 MHz Infinity NMR spectrometer using a 6.0 mm double-resonance MAS NMR probe operating at 68.01 MHz. The .sup.13C NMR spectra were acquired with cross polarisation (CP) magic-angle spinning (MAS) sequence with carbon background suppression. For all the samples 30,000 transients were accumulated, using a 1 ms contact time, 3 s recycle time and a spinning speed of 4.5 kHz. The chemical shifts were referenced to hexamethylbenzene (HMB) using the methyl signal (+17.35 ppm) as an external reference. .sup.29Si CP/MAS NMR measurements were performed with a Chemagnetics CMX 270 MHz Infinity NMR spectrometer using a 6.0 mm double-resonance MAS NMR probe operating at 53.73 MHz. For all the samples 80,000 transients were accumulated, using a 3 ms contact time, 3 s recycle time and a spinning speed of 4.5 kHz. The chemical shifts were referenced to tetrakis(trimethylsilyl)silane TTMSS using SiMe.sub.3 (−8.75, and −9.60 ppm) as an external reference.

Morphology and Roughness Assessment—Atomic Force Microscopy (AFM)

[0056] Topography and morphology of the CNF films before and after surface modification was studied by using Atomic force microscopy (AFM). AFM was carried out using a Nanoscope IIIa Multimode scanning probe microscope (Digital Instruments Inc., Santa Barbara, Calif., USA) in tapping mode. Images were scanned using silicon cantilevers supplied by μMasch (Tallin, Estonia) with nominal resonance frequencies of 320-360 kHz. Arithmetic and root mean square roughness values were extracted from topographic AFM images (1 μm*2 μm). No additional image processing other than flattening was performed on the images. Each sample was scanned in a minimum of three spots of each sample in order to assure reproducibility.

Contact Angle Measurements (CAM)

[0057] Changes in the wettability of the films after chemical modification were studied by CAM through the sessile drop method employing a CAM (KSV Instruments Ltd, Finland) equipped with a video camera and contact angle meter controlled with software. Measurements were determined by Young-Laplace equation approximation of the drop shape. Measurements were performed in at least 5 different sections for each sample.

Oxygen Transmission Rate Measurements

[0058] Oxygen transmission measurements were performed with Ox-Tran 2/20 Oxygen Transmission Rate System (Mocon, Modern Controls, Inc., USA) according to ASTM D3985-02. Tests were carried out at 23° C. and varying relative humidity using 100% oxygen as test gas. Aluminium foil masks, with an inner diameter area of 5 cm.sup.2, were used to mount film samples in the diffusion cell.

EXAMPLE 2

UV/Ozone Treatment (Österberg et al., 2013)

[0059] Nanofibrillated cellulose (NFC) was prepared by disintegration of fully bleached never-dried hard wood kraft pulp using a high shear Fluidizer (Microfluidics Int. Co, USA). The pulp was washed into sodium form prior to disintegration according to a method introduced by Swerin et al. (1990) and passed six times through the fluidizer. This treatment removes excess of salt from the pulp suspension and ensures that only sodium ions are associated with anionic groups on the pulp. No chemical or enzymatic pre-treatment was applied and the charge density of the pulp was 0.0065 meq/g as determined by conductometric titration according to Katz et al. (1984). The 132 cm.sup.2 large and around 100 μm thick free-standing NFC films were prepared by over-pressure filtration of a 0.84% dispersion of fibrils followed by hot pressing at 100° C. and 1,800 Pa (Österberg et al. 2013). Sefar Nitex polyamine fabric was used for filtration and remained with the film during pressing. A commercial UV ozonator from Bioforce Nanosciences was used to activate the NFC film surface. The nominal power of the UV source was 80 W, the intensities of the most important wavelengths were 199 for 185 nm and 3.975 for 254 nm according to the manufacturer. The distance between sample and radiation source was 2.5 cm. Treatment time for the films was 10 min. The sample size was about 2×4 cm.

[0060] Efficiency of the activation of the film surface was demonstrated by a simple silylation reaction performed on films obtained in pilot scale, according to Tammelin et al. (2011) and Peresin et al. (2012). The modification protocol is a slight variation of the method used to modify nanofibrils in bulk (Johansson et al. 2011). Films of about 100 mg were submerged in 150 ml Dimethylacetamide (DMA, 99%—Sigma-Aldrich) in a reaction vessel under continuous Nitrogen flow to evacuate any remaining oxygen. The film was kept in DMA under magnetic agitation until the temperature reached 80° C. Hexamethyldisilazan, (>99% purchased from Sigma-Aldrich) was added drop-wise while stirring (1 μl reagent/mg of film). Reaction was continued over night at constant temperature. Films were thoroughly washed with DMA and with methanol (HPLC grade; Rathburn) to remove any possible unreacted chemicals. Finally, the films were allowed to dry in air.

[0061] X-Ray Photoelectron Spectroscopy (XPS) (Kratos Analytical AXIS 165 electron spectrometer with monochromatic A1 Ka irradiation at 100 W), was used for surface chemical analysis of the free-standing NFC films. More specifically the effect of UV/O3 treatment and silylation on surface chemical composition was monitored. The measurement procedures and acquisition parameters were optimized for cellulosic samples as described by Johansson (2002). Samples were analysed after 1 week storage in desiccator. A minimum of three different areas were measured per sample. Atomic force microscopy (AFM) (Nanoscope IIIa scanning probe instrument from Digital Instruments, Santa Barbara, USA) was used to probe the surface topography of the films before and after UV/O.sub.3 treatment. Three different areas on each sample were scanned in tapping mode in air using silicon cantilevers (SCD 15/AIBS, MicroMasch, Tallinn, Estonia). The nominal resonance frequency of the cantilevers was around 300 kHz.

Contact Angle Measurements

[0062] The sessile drop method was employed for determination of water CA with a video camera based fully computercontrolled contact angle meter (CAM 200 from KSV Instruments Ltd., Finland). The measurements were performed at room temperature using deionized water further purified through a Milli-Q water purification unit. At least five separate measurements were made for each sample either 15 min or 1 week after UV/O.sup.3 treatment. The samples were stored in a desiccator prior to measurements.

[0063] Fourier transform infrared spectroscopy (FTIR) was applied to verify that no chemical degradation of the cellulose occur during the UV/ozone treatment. With the BIO-RAD UMA 500 spectrometer (USA) equipped with a universal attenuated total reflection (ATR) germanium crystal the films could be analysed directly without further sample preparation, the analysis depth being about one micrometer. The spectral data was processed with GRAMS AI software (Thermo Scientific, Galactic Industries Corporation, New Hampshire, USA. All spectra were base line corrected and further normalized to have the same value at 1,200 cm.sup.−1.

EXAMPLE 3

Chemical Modification with Chemical Vapour Deposition Technique

[0064] Thin (25-50 nm) Al.sub.2O.sub.3 coatings were deposited at low temperatures of 80 or 100° C. on various biobased CNF, pectin, PHB and PLA films. The depositions were carried out in a Picosun SUNALE™ ALD reactor. Trimethylaluminum (TMA, electronic grade purity, SAFC Hitech) and H.sub.2O were used as precursors. High purity nitrogen (99.9999% N.sub.2) was used as a carrier and purge gas. The deposition sequence was 0.1 s TMA pulse, 6 s N.sub.2 purge, 0.1 s water pulse and 6 s N.sub.2 purge. The operating pressure was 1-2 kPa. The resultant film growth rates were determined to be app. 0.1 nm/cycle on a silicon wafer Si(100). It should be emphasized, however, that because of the different polarities and functional groups of the surfaces of different polymers, the actual growth rates may deviate slightly from that determined for the Al.sub.2O.sub.3 coating on a flat silicon wafer.

Characterizations

[0065] The oxygen and water vapour barrier properties were determined for all the samples by measuring the oxygen and water vapour transmission rates. The oxygen transmission rate (OTR) was measured from two to three parallel samples using humid gases at 23° C. in 50% relative humidity with a Systech M8001 or Mocon Oxtran 2/20 and expressed as cm3/m2/105Pa/day. The water vapour transmission rate (WVTR) was measured for three to five parallel samples according to the modified gravimetric methods ISO 2528:1995 and SCAN P 22:68 and expressed as g/m.sup.2/day. The test conditions were 23° C. and 75% relative humidity.

Results

[0066] Both oxygen and water vapour barrier improvements were achieved for all bio-based substrates including CNF films with a 25 nm thick Al.sub.2O.sub.3 layer deposited by the TMA-H.sub.2O process (FIG. 2 and FIG. 3). In addition to extremely good oxygen barrier properties, it was noted that nanofibrillated cellulose (NFC) film coated with a 25 nm thick Al.sub.2O.sub.3 layer formed a highly homogenous layer on top of single fibres. This is believed to form protecting layers for nanofibres. Such materials are of high interest because of the controlled organic fibre and inorganic thin-film material integration. This kind of conformal coating on single fibres opens up new application possibilities in the area of filter development.

EXAMPLE 4

Plasma Activation and Deposition of CNF Films

[0067] CNF films were produced as follows: the dispersion including 30% of sorbitol was first carefully pre-homogenized by mixing with Diaf dissolver for 30 min (300 rpm) and then cast at a line-speed of 5 m/min onto a casting substrate using a specific feeding head. In the feeding head the dispersion formed an even and uniform wet layer. Spreading and adhesion between the substrate and aqueous CNF dispersion were carefully controlled by physical plasma-activation. Atmospheric plasma treatment unit Vetaphone Corona-Plus (Type TF-415, CP1C MKII 2.0 kW) equipped with argon/nitrogen plasma-unit was used to fix the surface energy of the casting substrate.

[0068] The films were further treated with HMDSO (hexamethyldisiloxane) plasma-deposition using Plasmaline® atmospheric plasma treatment unit and the following process parameters (P=600 W, N.sub.2 flow=2×150 SLM, HMDSO feed 2×1.5 SLM, line speeds 0.5, 5 and 10 m/min).

[0069] Water contact angles were measured using CAM200 equipment (KSV Instruments, Finland) in test conditions of 23° C. and 50% relative humidity. Water vapour transmission rates (WVTR) were determined gravimetrically using a modified ASTME-96B (wet cup) procedure. Samples with a test area of 30 cm.sup.2 were mounted on a circular aluminium dish (68-3000 Vapometer EZ-Cups), which contained water. Dishes were stored in test conditions of 23° C. and 50% relative humidity and weighed periodically until a constant rate of weight reduction was attained.

[0070] Both surface hydrophobicity (FIG. 4) and water vapour barrier properties (FIG. 5) were increased as a result of HMDSO plasma-deposition.

CITATION LIST

Patent Literature

[0071] 1. WO 2013/060934

Non-Patent Literature

[0072] 1. Solala, I., Volperts, A., Andersone, A., Dizhbite, T., Mironova-Ulmane, N., Vehniainen, A., Pere, J., and Vuorinen, T., “Mechanoradical formation and its effects on birch kraft pulp during the preparation of nanofibrillated cellulose with Masuko refining,” Holzforschung 66(4), pp. 477-483 (2011). [0073] 2. Johansson, L.-S., Tammelin, T., Campbell, J. M., Setala, H., Österberg, M., Experimental evidence on medium driven cellulose surface adaptation demonstrated using nanofibrillated cellulose. Soft Matter 2011, 7, 10917-10924. [0074] 3. Österberg, M., Soledad Peresin, M., Johansson, L.-S., Tammelin, T., Clean and reactive nanostructured cellulose surface, Cellulose 2013, 20, pp. 983-990, DOI: 10.1007/s10570-013-9920-8.